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Cu and Cu-Based Nanoparticles: Synthesis and Applications in

Catalysis
Manoj B. Gawande,*,† Anandarup Goswami,†,‡,§ François-Xavier Felpin,∥ Tewodros Asefa,‡,§
Xiaoxi Huang,‡ Rafael Silva,⊥ Xiaoxin Zou,# Radek Zboril,*,† and Rajender S. Varma*,†
†
Regional Centre of Advanced Technologies and Materials, Faculty of Science, Department of Physical Chemistry, Palacky University,
Šlechtitelů 11, 783 71 Olomouc, Czech Republic
‡
Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, 610 Taylor Road, Piscataway, New
Jersey 08854, United States
§
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Department of Chemical and Biochemical Engineering, Rutgers, The State University of New Jersey, 98 Brett Road, Piscataway, New
Jersey 08854, United States
∥
UFR Sciences et Techniques, UMR CNRS 6230, Chimie et Interdisciplinarité: Synthèse, Analyse, Modélisation (CEISAM),
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Université de Nantes, 2 Rue de la Houssinière, BP 92208, Nantes 44322 Cedex 3, France

⊥
Department of Chemistry, Maringá State University, Avenida Colombo 5790, CEP 87020-900 Maringá, Paraná, Brazil
#
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, International Joint Research Laboratory of Nano-Micro
Architecture Chemistry, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, China

ABSTRACT: The applications of copper (Cu) and Cu-based nanoparticles, which are
based on the earth-abundant and inexpensive copper metal, have generated a great deal
of interest in recent years, especially in the field of catalysis. The possible modification of
the chemical and physical properties of these nanoparticles using different synthetic
strategies and conditions and/or via postsynthetic chemical treatments has been largely
responsible for the rapid growth of interest in these nanomaterials and their applications
in catalysis. In addition, the design and development of novel support and/or
multimetallic systems (e.g., alloys, etc.) has also made significant contributions to the
field. In this comprehensive review, we report different synthetic approaches to Cu and
Cu-based nanoparticles (metallic copper, copper oxides, and hybrid copper
nanostructures) and copper nanoparticles immobilized into or supported on various
support materials (SiO2, magnetic support materials, etc.), along with their applications
in catalysis. The synthesis part discusses numerous preparative protocols for Cu and Cu-based nanoparticles, whereas the
application sections describe their utility as catalysts, including electrocatalysis, photocatalysis, and gas-phase catalysis. We believe
this critical appraisal will provide necessary background information to further advance the applications of Cu-based
nanostructured materials in catalysis.

CONTENTS 4. Catalytic Applications of Cu NPs in Organic

Transformations 3743
1. Introduction 3723 4.1. Azide−Alkyne Cycloaddition via Click Chem-
2. Scope of This Review 3723 istry 3743
3. Synthesis and Characterization 3724 4.2. Coupling Reactions 3745
3.1. Cu and Copper Oxide (CuOx) NPs 3724 4.3. Reduction Reactions 3755
3.2. Supported Cu-Based NPs 3731 4.4. Oxidation Reactions 3758
3.2.1. Carbon-Supported Cu-Based NPs 3731 4.5. “One-Pot” Multicomponent Reactions 3762
3.2.2. Metal Oxide-Supported Cu NPs 3735 4.6. Miscellaneous Reactions 3767
3.2.3. Polymer-Supported Cu NPs 3736 5. Photocatalysis 3772
3.2.4. Silica- or Silicon-Supported Cu NPs 3739 5.1. Cu and Copper(II) Oxide/Hydroxide NPs as
3.2.5. Zeolite-Supported Cu NPs 3739 Cocatalysts for the Hydrogen Evolution
3.3. Other Cu-Based NPs 3739 Reaction (HER) 3773
3.4. Growth Mechanisms of Cu NPs 3740 5.2. Copper(I) Oxide NPs for HER 3774
3.4.1. Growth of Cu NPs 3740
3.4.2. Growth of CuOx NPs 3741
3.4.3. Growth of Other Cu-Based NPs 3742
3.5. Characterization 3742 Received: August 14, 2015
Published: March 3, 2016

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5.3. Cu and CuOx NPs as Cocatalysts for the CO2 Cu is a 3d transition metal and has some interesting physical
Reduction Reaction 3775 and chemical properties.32 Cu-based materials can promote and
5.4. CuOx-Based NPs for Self-Cleaning 3776 undergo a variety of reactions due to Cu’s wide range of
5.5. Cu NPs as Plasmonic Photocatalysts for accessible oxidation states (Cu0, CuI, CuII, and CuIII), which
Organic Transformations 3776 enable reactivity via both one- and two-electron pathways.
6. Electrocatalysis 3777 Because of their unique characteristics and properties, Cu-based
6.1. Electrocatalysis of Fuel-Cell-Related Reac- nanocatalysts have found many applications in nanotechnology,
tions 3778 including catalytic organic transformations, electrocatalysis, and
6.2. Reduction of CO2 to Liquid Fuels 3779 photocatalysis.33−46 The main challenge in the development of
6.3. Water Splitting 3781 catalytic NPs is to prepare nanomaterials that are highly active,
6.4. Cu MOFs (Metal−Organic Frameworks) as selective, stable, robust, and inexpensive.47,48 One economical
Electrocatalysts 3782 way of creating advanced Cu-based nanomaterials for catalysis
7. Gas-Phase Catalysis 3782 is to anchor Cu NPs (e.g., Cu, CuO, or Cu2O) on supports
7.1. NOx Reduction 3783 such as iron oxides, SiO2, carbon-based materials, or polymers.
7.2. CO Oxidation 3784 Additionally, Cu’s high boiling point makes it compatible with
7.3. Water−Gas Shift Reaction 3785 high-temperature and -pressure chemical reactions, including
8. Conclusions and Future Scope 3786 continuous flow reactions, microwave-assisted reactions, vapor-
Author Information 3788 phase reactions, and various organic transformations.49−53 Such
Corresponding Authors 3788 unique properties, conducive for the development of reactive
Notes 3788 and selective catalytic systems, have made Cu and its alloys
Biographies 3788 among the most valuable metals in the past, and will ensure that
Acknowledgments 3789 they remain important in the future.
Abbreviations 3789
References 3790 2. SCOPE OF THIS REVIEW
Despite sporadic attempts, there is no systematic and
comprehensive overview covering the established catalytic
uses of Cu-based NPs.33 This review discusses the uses of Cu
1. INTRODUCTION and Cu-based NPs as catalysts for diverse reactions, including
The catalytic activity of nanoparticles (NPs) represents a rich reduction, oxidation, A3 coupling, electrocatalysis, photo-
resource for chemical processes, employed both in industry and catalysis, and gas-phase reactions (Figure 1). The synthetic
in academia.1,2 NPs have applications in diverse fields, including
energy conversion and storage, chemical manufacturing,
biological applications, and environmental technology.3,4 The
great interest in catalysis using nanomaterials has prompted the
synthesis and investigation of diverse highly functionalized NPs,
including graphene-based catalysts, nanocarbon catalysts, core/
shell nanocatalysts, magnetite-supported nanocatalysts, inte-
grated nanocatalysts, and also various metal nanostructures.5−16
The study of these systems has been facilitated by rapid
developments in synthetic methodology that have enabled the
preparation of NPs with tunable compositions, shapes, sizes,
and structures, either on their own or supported on other
materials.17−24
Nanomaterials prepared from earth-abundant and inexpen-
sive metals have attracted considerable attention because of
their potential as viable alternatives to the rare and expensive Figure 1. Applications of Cu-based nanocatalysts.
noble-metal catalysts used in many conventional commercial
chemical processes.25 These metal NPs often exhibit activity
different from that of the corresponding bulk materials because
of their different sizes and shapes, which give rise to distinctive strategies and relevant examples of Cu and Cu-based NPs are
quantum properties. In this context, Cu NPs are particularly discussed with brief descriptions of relevant characterization
attractive because of copper’s high natural abundance and low techniques such as X-ray diffraction (XRD), scanning electronic
cost and the practical and straightforward multiple ways of microscopy (SEM), high-resolution transmission electronic
preparing Cu-based nanomaterials.26−31 microscopy (HR-TEM), UV−vis spectroscopy, X-ray photo-
Despite the strong background on the applications of bulk electron spectroscopy (XPS), and atomic absorption spectros-
Cu in various fields (e.g., optics, electronics, etc.), the use of Cu copy (AAS). We believe that a detailed overview of the
NPs is restricted by Cu’s inherent instability under atmospheric established procedures for preparing Cu NPs and their
conditions, which makes it prone to oxidation. Many efforts to applications would be helpful to a broad community of
develop the methods and supporting materials that increase the scientists working in the fields of nanotechnology, chemical
stability of Cu NPs by altering their sensitivity to oxygen, water, engineering, organic chemistry, inorganic chemistry, and
and other chemical entities has encouraged the exploration of materials chemistry. In addition, most of the chemistries
alternative Cu-based NPs with more complex structures, such detailed in this review, namely, reactions in benign media, such
as core/shell Cu NPs or systems based on copper oxides. as water, high turnover numbers (TON) and turnover
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frequencies (TOF), and magnetic recyclability will address
current important developments in the field.
3. SYNTHESIS AND CHARACTERIZATION
To simplify our overview of the synthesis of Cu and Cu-based
NPs, we have grouped them into three different categories: (i)
Cu and copper oxide (CuOx) NPs, (ii) supported Cu-based
NPs, and (iii) other Cu-based NPs (vide infra). The discussion
of materials in the first category covers the synthesis of Cu
metal and or copper oxide NPs. This section emphasizes the
synthetic protocols which are prevalent in the literature. In the
second category, the preparations of Cu and Cu-based NPs on
supported systems are emphasized, focusing more on the
diversity and the versatility of support materials. Despite some
recent efforts,33 and the considerable recent progress in the
development of supported catalysts, the literature currently
lacks such a systematic review of this field. The final part of this
section focuses on the synthesis of other Cu-containing NPs,
including metal alloys and multimetallic systems. The main
objective of this section is to review the procedures that have
been used to synthesize Cu and Cu-based NPs with special
emphasis on recent examples. Three tables are presented,
listing the reported synthetic strategies for preparing materials
in each of the three categories. In the “product description”
columns in all three tables, Cu-based species (Cu-oxides and
others) are specifically described, whereas the entries without
any such mentions represent that the corresponding synthetic
procedures lead to the formation of Cu NPs.
3.1. Cu and Copper Oxide (CuOx) NPs
Procedures for synthesizing Cu-based NPs generally rely on the
same techniques that have been used to prepare other metal
NPs. Most methods are either “bottom-up” (in which atomic-
level precursors are used to synthesize nanosized materials) or
“top-down” (in which a bulk solid is broken down into
progressively smaller components). While both approaches
have their advantages and disadvantages, the bottom-up
approach has become more popular because it offers greater
scope for controlling the shape and size of the resulting
NPs.54−57 In addition, the susceptibility of Cu NPs to undergo
oxidation allows the formation of more stable copper oxide NPs
in many cases. The difficulty in classifying the synthetic
techniques for the formation of such nanomaterials mainly
stems from the similarity of the associated chemical processes.
The synthesis of Cu and copper oxide NPs essentially centers
around mainly four chemical reaction types, namely, (1)
reduction, (2) hydrolysis, (3) condensation, and (4) oxidation.
Depending on the choice of final materials, either one or a
combination of aforementioned chemistries can be applied. The
synthesis of Cu NPs often entails the reduction of Cu(I) or
Cu(II) sources. The synthesis of copper oxide NPs, on the
other hand, basically requires hydrolysis of the precursors
followed by a dehydration process leading to the final materials.
Additionally, an oxidation process (sometimes unavoidable for
Cu-based NPs) can be deployed for the preparation of Cu-
based NPs with higher oxidation numbers from their respective
precursors of lower oxidation states. In synthetic processes, the
techniques that are applied provide a suitable environment and
energy to facilitate the process of choice while additional
constraints are imposed to modulate the stability, properties,
and morphology of the final NPs. On the basis of the literature
precedence, the methods for synthesizing Cu-based nanoma-
terials can be classified into five major categories (Figure 2):
3724
Review
Figure 2. Major synthetic approaches for the preparation of Cu-based
nanomaterials (MW = microwave, CVD = chemical vapor deposition,
ALD = atomic layer deposition, IL = ionic liquid, and DBD = dielectric
battery discharge).
chemical treatment, electrochemical synthesis, photochemical
techniques, sonochemical methods, and thermal treatment. The
section labeled “others” includes relatively sophisticated
procedures that have been reported recently and are receiving
increasing attention.
Among these, the most popular procedure is based on
“chemical treatment”, and some of the more modern methods
could be regarded as an extension of this protocol providing
advantages in terms of shape and/or size selectivity. The
following section briefly discusses some of the important
examples for the synthesis of Cu NPs (where, in most cases,
external reducing agents have been used) and copper oxide
NPs. Depending on the materials, reaction environments, and
synthetic methods involved, this section can be broadly divided
into several subcategories: wet chemical, reverse micelle, MW-
assisted, and biosynthesis and IL-assisted methods. The results
of a thorough survey of the literature in this area are
summarized in Table 1.
The “wet chemical” technique is a long-established approach
for the preparation of metallic Cu NPs mostly involving
reducing agents that provide electrons for the reduction of Cu
salts (such as CuSO4, copper(II) acetylacetonate,58 CuCl2,59 or
Cu(NO3)2). Reducing agents used for this purpose often
include sodium borohydride,59 hydrazine,60−62 1,2-hexadecane-
diol,58 glucose,63 ascorbic acid,64−66 CO,90 or more recently
introduced borane compounds.48 Various capping agents have
also been used to stabilize the ensuing Cu NPs and to control
the particle growth.
An alternative approach is the so-called “reverse micelle
method”, which involves the formation of an oil-in-water (O/
W)-type microemulsion by adding a surfactant to a vessel
containing otherwise-immiscible polar and nonpolar sol-
vents.171 Figure 3 shows the typical structure of a reverse
micelle, featuring hydrocarbon tails that project into the oil
phase and a sphere of polar head groups that encapsulate a
small quantity of the aqueous phase in an inner core. Such
reverse micelles can serve as uniformly sized nanoreactors for
NP production that enable precise control over the shape and
size of the ensuing nanomaterials.171 By tuning the reaction
conditions to produce micelles of different sizes, one can adjust
the size of the resulting NPs.91−96 For instance, following the
methods initially developed by Chen and co-workers,172 Rivas
and co-workers94 synthesized metallic Cu nanoclusters using a
microemulsion system prepared by mixing the surfactant SDS
(sodium lauryl sulfate or sodium dodecyl sulfate) with the
cosurfactant isopentanol, cyclohexane as the oil phase, and an
aqueous solution of CuSO4 as the copper source. After removal
of oxygen from the system by purging with nitrogen, a dilute
solution of aqueous sodium borohydride was added to allow
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Table 1. Reported Methods for the Synthesis of Cu and Copper Oxide NPs

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Table 1. continued

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Table 1. continued

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Table 1. continued

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Table 1. continued

the formation of colloidal Cu clusters, and finally colloidal Cu
NPs.
An expeditious newer approach called microwave (MW)-
assisted synthesis, which uses microwaves as an alternate energy
source for the reaction, has been utilized for the synthesis of
3729
Cu-based NPs. In this process, the reaction mixture is irradiated
with microwaves whose electromagnetic energy gets converted
into heat, accelerating the synthesis of Cu-based NPs. This
process offers several advantages compared to traditional
heating methods such as noncontact heating, quick energy
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Figure 3. A typical reverse micelle.
transfer, or material-selective heating, etc.,173,174 and often
allows reactions to proceed at much higher rates than can be
achieved by conventional heating. Yin and co-workers
developed a rapid microwave-based method for the preparation
of metallic Cu NPs by reduction of CuSO4·5H2O with
NaH2PO2·H2O in ethylene glycol.98 This procedure offers
high reaction rates and yields a product with a narrow particle
size distribution. Kawasaki et al. reported the preparation of
fluorescent 2 nm Cu nanocrystals via MW-assisted polyol
synthesis, which was performed in a nonaqueous solvent to
avoid oxidation of the Cu surface.99 A similar report revealed
that MW irradiation of a solution containing copper
acetylacetonate in benzyl alcohol produced crystalline Cu
nanospheres that were 150 nm in size and stable in air for a few
months.100 Similarly, Cu2O105 and CuO103 NPs have also been
prepared utilizing MW energy.
Another rapidly emerging method that requires special
mention utilizes the plant-derived extracts that serve both as
reducing and/or capping agents. For instance, an extract from
the plant Terminalia arjuna was used to reduce Cu(NO3)2
under the MW irradiation conditions,101 and an extract from
the leaves of henna (Lawsonia inermis) could reduce Cu(II) salt
(CuSO4·5H2O).108 Under these conditions, the biomolecules
in the extract served as capping agents, resulting in the
formation of stable Cu NPs. These methods have also been
successfully applied to synthesize copper oxide-based nanoma-
terials,114,116 in which such bioextracts acted mostly as capping
agents/stabilizers.
Among other methods, ionic-liquid (IL)-assisted synthesis of
Cu-based nanoparticles has gained attention because of the
unique solvating and other physicochemical properties of
ILs.175−177 A relatively straightforward “top-down” approach to
Cu NP synthesis was reported by Kim et al., who prepared
nanoparticles with diameters of 20−200 nm by simply stirring
Cu microparticles (1−5 μm in diameter) in the IL 1-butyl-3-
methylimidazolium tetrafluoroborate (BMIM+BF4−).118 This
caused the Cu microparticles to dissociate into NPs because of
the strong interaction between the Cu surface and the IL’s
anionic components, as shown in Figure 4. A similar method
was employed by Han et al. to prepare Cu NPs using other ILs
such as 1-butyl-3-methylimidazolium hexafluorophosphate
(BMIM+PF6−) and 1-ethyl-3-methylimidazolim tetrafluorobo-
rate (EMIM+BF4−).119 A more recent report demonstrated that
the reaction times required for such syntheses could be reduced
by using the IL BMIM+NO3−,120 whose anions are mostly in
the free ion state, facilitating the efficient dissociation of Cu
flakes.
3730
Review
Figure 4. Ionic-liquid-induced dissociation of Cu microparticles into
nanoparticles. Reprinted from ref 118. Copyright 2009 American
Chemical Society.
Utrasonic frequencies between 20 kHz and 15 MHz have
also been used to synthesize various nanostructures. Sonication
promotes chemical reactions via acoustic cavitation, in which
minute bubbles are formed and then implode in a way that
generates very high localized temperatures and pressures.
Sonochemical techniques make it possible to prepare nanoma-
terials under ambient conditions without the need for high
temperatures, high pressures, or extended reaction
times.125,178,179 Sabbaghzadeh and co-workers reported a
sonication-based protocol for preparing monodisperse metallic
Cu NPs of different sizes using ethylene glycol as a capping
agent and hydrazine monohydrate as the reducing agent;
sonication made it possible to avoid the formation of
polydispersed Cu materials.123 A similar protocol has been
used to prepare amorphous Cu NPs, nanocrystalline Cu2O
embedded in a polyaniline matrix,124 and NPs based on
CuO,125 Cu2O,125 and copper hydride.180
Photonic energy, especially in the form of lasers, can offer an
advantage for the synthesis of high-purity metal NPs with
specific shapes and chemical compositions.129 This predom-
inantly “top-down” synthetic approach was used by Shimotsu-
ma et al. to synthesize Cu nanomaterials from Cu flakes.
Subsequently, nanowires and nanospheres of 50 nm were
prepared from the initial flakes via ultrafast pulse laser
irradiation by taking advantage of the energy generated from
the interference between the laser light field and the surface
plasmon polariton waves.130 In another study, Mahdi and co-
workers synthesized Cu NPs in virgin coconut oil using a laser
ablation technique;131 the setup of their apparatus is shown in
Figure 5. Laser ablation has also been recently used to make
similar Cu NPs in various solvents, including water,132,133
acetone,132,133,181 and ethanol.132
Electrochemical synthesis has attracted considerable atten-
tion in nanomaterial fabrication mainly due to its low cost, low-
temperature operation, high product purity, simplicity, and
environmental friendliness.182−184 In electrochemical syntheses
of Cu-based nanomaterials, a steady current flow is applied
through an electrolytic cell containing an aqueous solution of a
Cu salt such as CuSO4. This causes electrons to be transferred
from the anode to the cathode, where the Cu ions are reduced
to Cu atoms that subsequently agglomerate to form Cu NPs.96
In another case, electrochemical deposition was used to
synthesize finer Cu NPs than were obtainable by chemical
reduction, with control over the products’ size.97 In addition, it
is also possible to obtain Cu NPs with specific morphologies by
performing electrochemical synthesis in the presence of
templates. For example, electrochemical deposition was used
to prepare Cu nanowires by confining a CuSO4 solution within
the nanochannels of porous anodic alumina templates.136 Yang
et al. have prepared Cu nanorods (with diameters of around 30
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Figure 5. Laser ablation system for preparing Cu NPs, comprising a
laser, a lens, a cell, a stirrer, a Cu target, and a N2 tank. The fluid cell is
double-shelled and connected to a supply of N2 gas, which passes
through virgin coconut oil and escapes through the outlet valve.
Reprinted with permission from ref 131. Copyright 2013 Materials
Research Society.
nm and lengths of 400−1000 nm) via an electrochemical
method in the presence of surfactants, which serve as both
templates and stabilizers.137
It is relatively difficult to put “thermal treatment” as a
separate procedure because other methods often involve
heating (in one form or another) during the syntheses of Cu-
based nanomaterials (especially copper oxides). However, in
view of the substantial reports of such thermal treatment, which
not only entails thermal degradation but also high-temperature
heat treatment of different Cu precursors, this type of synthesis
deserves a separate discussion. Thermal decomposition is
among the most widely used methods in this category. For
instance, the thermal decomposition of bis(2-hydroxy-1-
naphthaldehydato)copper(II) in the presence of oleylamine as
a capping agent was used to prepare metallic copper
nanocrystals.144 The same group also reported the preparation
of 40 nm Cu NPs via the thermal decomposition of copper
oxalate145 as well as the thermal synthesis of Cu and Cu2O NPs
from bis(salicylidiminato)copper(II).146 Similarly, a copper
oleate complex prepared by the reaction of CuCl2 and an
aqueous solution of sodium oleate was used as a precursor in
the thermal synthesis of well-dispersed Cu NPs.148,149 Garcia-
Cerda reported the synthesis of Cu NPs by thermal
decomposition of copper oleate using phenyl ether,150 whereas
the thermal decomposition of copper(II) acetylacetonate
reportedly afforded Cu and copper oxide NPs.151,152
Apart from previously described methods, with the advance-
ment of sophisticated instrumentation, the field keeps
witnessing different techniques embodying various deposition
techniques (atomic layer deposition (ALD),163 etc.), chemical
dealloying,168 dielectric battery discharge (DBD),169 and the
recrystallization-induced self-assembly (RISA)170 process,
among others.
The aforementioned sections and Table 1 provide an
extensive review of the different synthetic methods available
for making the Cu and Cu-based nanoparticles. “Chemical
treatment” pertains to methods in which Cu precursors are
treated with external reagents that lead to Cu and Cu-based
3731
Review
nanoparticles. The vast availability of reducing and capping
agents, different synthetic environments, and simpler laboratory
techniques make this category relatively economical and user-
friendly. In this class, the reaction parameters play important
roles in determining the shape, size, and composition of the
final nanomaterials. In addition to the reagents, by providing
appropriate energy input (through thermal or MW-assisted
methods) and modifying the reaction environments (with
reverse micelles or ionic liquids) for the reactions, the process
can be made more selective for specific products. Moreover,
greener synthetic approaches using naturally abundant plant
extracts as reducing and/or as capping agents (biosynthesis)
have been utilized. Decomposition of Cu precursors at a
relatively high temperature (calcination or pyrolysis) has also
been fruitful for the generation of such species, especially
copper oxide species (thermal treatment). The use of alternate
energy sources offers the synthesis of nanoparticles with
uniform, small sizes (e.g., sonochemical, photochemical,
electrochemical, etc.) from their respective precursors. For
example, in the case of electrochemical synthesis, the rate of
reduction of Cu species can be controlled by varying the
voltage used, which in turn can lead to a variety of Cu and
CuOx nanoparticles. Barring the above-mentioned methods, the
relatively sophisticated deposition and sputtering techniques
provide more size-selective synthesis of Cu and Cu-based
nanoparticles. In this respect, the experimental conditions as
well as the type of copper precursors play a controlling role in
the final outcome. The rational choice of the synthetic
technique is becoming increasingly important to design such
nanoparticles with the desired shape, size, and morphology for
various applications and to study their structure−activity
relationships.
3.2. Supported Cu-Based NPs
As mentioned in the Introduction, special attention should be
given to the materials used to support Cu and Cu-based NPs
because the interactions between the NPs and support can have
profound effects on the resulting material’s physical and
chemical properties. Consequently, by choosing an appropriate
support, it is possible to tailor the properties of the NPs to suit
specific applications. In this section, supporting materials for Cu
NPs are categorized on the basis of their fundamental chemical
compositions, and subcategorized on the basis of their
prevalence and utility. Representative examples are given for
each category, and a comprehensive list of supporting materials
described in the literature to date is provided in Table 2.
3.2.1. Carbon-Supported Cu-Based NPs. Recent ad-
vances in the use of metal-embedded carbon networks,
especially in electrocatalysis, have prompted the exploration
of several carbon-based materials as supports for Cu NPs. One
such supporting material is activated carbon, which has been
used in a number of applications. For example, Alonso et al.
prepared Cu NPs on activated carbon187,248−250 by stirring
activated carbon with a freshly prepared Cu NP solution. The
NPs were prepared by reducing anhydrous CuCl2 with Li metal
in THF containing a small amount of 4,4′-di-tert-butylbiphenyl
(DTBB; 10 mol %) for a few minutes at room temperature.
The resulting supported Cu NPs efficiently catalyzed a range of
reactions without needing any pretreatment. Eskandari and co-
workers described the preparation of Cu NPs on activated
carbon via a two-step procedure;191,251 activated carbon was
initially refluxed in nitric acid solution for a few hours, and the
ensuing oxidized carbon material was than refluxed in an
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Table 2. Results of a Comprehensive Literature Survey of Methods for the Synthesis of Supported Cu and Cu-Based NPs

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Table 2. continued

anhydrous ethanolic solution of CuI under a nitrogen
atmosphere.
Among carbon support materials, carbon nanotubes (CNTs)
offer unique advantages because of their interesting physical
3734
and chemical properties, which include high surface area, high
conductivity, numerous possibilities of surface functionalization,
and the inherent capability of incorporating the guest materials
owing to their unique hollow geometry.252−254 Incorporating
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metal NPs into carbon nanotube structures makes it possible to
combine the useful properties of carbon nanonetworks and
metal NPs.255−258 Wang et al. have reported the preparation of
Cu NP-decorated carbon nanotubes, with the NPs either
occupying the nanotubes’ inner cavities or coating their exterior
surfaces.202 The hybrid nanostructures were prepared by
treating carbon nanotubes with concentrated HNO3 and then
mixing them with a solution of Cu(NO3)2 under sonication and
magnetic stirring. After subsequent washing and drying, the
intermediate products were calcined at 623 K under an argon
atmosphere for 3 h to afford the final products. In this study,
nanotubes with Cu NPs coating on their external surfaces were
obtained by using end-closed nanotubes instead of open-ended
ones. In another study, N-doped carbon nanotubes were
prepared by taking carbon nanotubes that had been preoxidized
with HNO3 and heating them in the presence of ammonia.203
The resulting N-doped nanotubes were then reacted with a
solution of copper acetate to load them with Cu NPs,203 a
process facilitated by the strong interactions between nitrogen
centers and metals. Carbon nanotubes have also been used as
solid supports for Cu NPs in a range of applications.200,259,260
Graphene has been recognized as an attractive catalyst
support for some time, largely because of its extremely high
surface area (∼2600 m2/g), high thermal/electrical conductiv-
ity, and chemical stability.188 Graphene-supported Cu NPs have
been synthesized using various methods that typically involve
mixing a solution of graphene oxide and a Cu salt and then
reducing them together.188 For example, Guo et al. prepared
metallic Cu NPs on graphene sheets by reducing Cu2O/
graphene composites in a mixture of H2 (5 vol %) and argon at
500 °C.192 Composites of reduced graphene oxide (rGO)
decorated with Cu NPs have also been prepared by mixing a
solution of rGO with Cu NPs and heating at 110 °C for 12
h.190 Graphene sheets adorned with Cu NPs were synthesized
by electrodepositing the nanoparticles on the graphene with a
modified glass carbon electrode.199
Graphite, another important carbon-based support, is a
precursor for graphene where the interlayer interactions can be
destroyed to offer single-layer or multilayer graphene.261 Due to
their potential of having covalent and noncovalent interactions
with other materials as well as relatively high natural
abundance, graphitic materials have been utilized in diverse
applications,262 including a benign and inexpensive support for
CuO NPs. Felpin and co-workers have developed a simple
procedure for the preparation of CuO NPs on graphite by
stirring a solution of Cu(OAc)2 and graphite in anhydrous
degassed methanol (MeOH) under an atmosphere of H2 (1
atm) for 12 h.263 Filtrations over a membrane or a glass filter
provided the ready-to-use solid catalyst with no need for further
treatment. This simple procedure yielded well-dispersed
spherical CuO NPs with a crystallite size of <5 nm. Recently,
an improved procedure enabled the synthesis of graphite-
supported ultrasmall Cu(OH)2 NPs with an average diameter
of 2 nm.264
Diamond NPs (npD) have also been used as supports for
catalytically active metals because of their stable and inert sp3-
carbon-based networks.265 Initially, their preparation proved
challenging because the npD surface is too inert to bond
efficiently with most catalysts. To increase their surface
reactivity, the diamond NPs were treated with the Fenton
reagent (Figure 6), which removed amorphous carbonaceous
soot (thereby preventing aggregation) and generated additional
surface hydroxyl groups to enable bonding with the supported
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Review
Figure 6. Functionalization of a diamond nanoparticle’s surface by the
Fenton reaction. Reprinted from ref 266. Copyright 2009 American
Chemical Society.
catalysts.265,266 Dhakshinamoorthy et al. have prepared Cu NPs
supported on Fenton-treated diamond NPs186 in which surface
defects were removed or made less pronounced by annealing
the materials under a continuous flow of hydrogen gas at 500
°C for 6 h. Diamond NPs with or without annealing were then
used to support Cu NPs prepared from Cu(NO3)2·2H2O.
3.2.2. Metal Oxide-Supported Cu NPs. A variety of metal
oxides have been examined as supporting materials for Cu-
based NPs and related nanomaterials. The choice of support
largely depends on the ease of its synthesis, its compatibility
with different substrates/reagents, and, most importantly, the
properties it confers on the resulting supported nanomaterials.
Ceria is an important support material for various catalysts
due to its oxygen content, which is particularly high at its
surfaces.267 A Cu/CeO2 hybrid nanocatalyst prepared by
depositing Cu NPs onto hexamethylenediamine-capped ceria
nanocubes has been used to promote CO oxidation.268
Moreover, CuO NPs have been prepared on a CeO2 support
and used as a highly efficient and green recyclable catalyst.269
Rothenberg and co-workers synthesized supported Cu−ceria
catalysts by subjecting a mixture of Ce(NO3)·H2O and
Cu(NO 3 )·3H 2 O to sequential co-melting, drying, and
pyrolysis.218
Another important support material that has been widely
used as a support for NPs is alumina. Choudary and co-workers
have reported the synthesis of alumina-supported Cu NPs from
copper(II) acetylacetonate and aluminum isopropoxide pre-
cursors using an aerogel-based method,228 while Park et al. have
developed a Cu catalyst by immobilizing Cu NPs on aluminum
(oxy)hydroxide [AlO(OH)] fibers as shown in Figure 7.214,270
Figure 7. Preparation of an alumina-supported Cu nanocatalyst.
Owing to its Lewis acidic nature, zinc oxide NPs have been
employed in catalysis, mostly as catalysts themselves but
sometimes also as supports for other nanocatalytic species. For
example, Schlögl and co-workers have prepared Cu/ZnO
catalysts from hydroxycarbonate precursors (Figure 8).271 In a
template-free synthetic technique, Cu NPs supported on ZnO
nanorods (NRs) were synthesized by growing ZnO nanoarrays
in a microchannel reactor, adding aqueous solutions of Cu(II)
salts, and then reducing the resulting mixtures.209 Recently,
Cu/ZnO microball catalysts were prepared via a two-step
process in which ZnO nanorods were grown hydrothermally
and then combined with preformed Cu NPs.220 In a separate
study, Karelovic et al. synthesized Cu/ZnO catalysts via citrate
decomposition.272
Another metal oxide that has been widely explored as a
support for Cu NPs is MgO. Burri and co-workers prepared a
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Figure 8. Procedure for preparing Cu/ZnO catalysts from
hydroxycarbonate precursors. Reprinted with permission from ref
271. Copyright 2003 Wiley-VCH Verlag GmbH & Co. KGaA.
MgO support by calcining Mg(NO3)2·6H2O with K2CO3 at
723 K for 12 h and then impregnated the resulting material
with Cu NPs to obtain a Cu@MgO catalyst.221,224
Mainly because of its unique photochemical properties,
titania has been used extensively to support various nanoma-
terials. For example, Chang and co-workers synthesized titania-
supported Cu NPs via an alkoxide wet chemical process.225
Pasini et al. have reported the preparation of titania-supported
Cu NPs by immobilizing premade monometallic Cu species on
TiO2,273 a technique also applicable to copper oxide NPs. Yus
and co-workers prepared oxidized Cu NPs (which mainly
consisted of Cu2O) on titania and other materials by adding the
support (TiO2, MgO, etc.) to a suspension of freshly prepared
NPs.274 Liu et al. synthesized TiO2 nanotubes decorated with
Cu NPs by exploiting palladium activation to facilitate Cu or
copper oxide deposition.210 The nanotubes were initially
activated by being dipped in a solution of 8.9 × 10−4 M
Pd(OAc)2 in 10% acetic acid, followed by another immersion in
0.2 M NaH2PO2 solution. After the activation step, the copper
nanoparticles were deposited by mixing the nanotubes with a
solution of CuSO4·5H2O, KNaC4H4O6·4H2O, and form-
aldehyde under sonication. The resulting material was then
washed with water and dried at 393 K.
Because they can be prepared using protocols similar to
those used for titania-supported materials, zirconia-supported
Cu NPs have also received significant attention in recent times.
Rao and co-workers reported the preparation of Cu-loaded
zirconium oxide by impregnating a ZrO2 support with a suitable
quantity of Cu(NO3)2·3H2O.227 The resulting material was
then dried and pyrolyzed at 773 K for 5 h in air to afford copper
oxide supported on zirconium oxide. Similar materials have also
been described previously.222,275
While expensive, lanthanum oxide has unique Lewis acidic
properties that are beneficial in various catalytic applications.
Shen and co-workers prepared La2O3-supported Cu NPs by a
deposition−precipitation method as shown in Figure 9.223
Similarly, Azambre et al. have reported the synthesis of Cu−
VOx multiwalled nanotubes by exchanging the protonated
template in the parent dodecylamine−VOx nanotubes with
Cu(II) salts.276
Recent developments have resulted in the identification of a
range of new support materials that can host Cu NPs. Some
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Review
Figure 9. Preparation of Cu/La2O3 catalysts.
examples are mentioned in the following section with an
extensive survey of literature provided in Table 2.
Metal−organic frameworks (MOFs) are porous crystalline
materials comprising a three-dimensional framework of metal
ions or metal clusters linked by rigid bi- or multi-podal organic
linkers. They have a number of interesting properties, including
porosity, crystallinity, and relatively strong metal−ligand
coordination bonds.277 A recent publication described the use
of MOFs as supports for Cu nanomaterials. In that study, Jiang
and co-workers prepared Cu NPs loaded in a MIL-101 (Cr)
metal−organic framework and utilized the resulting material as
a heterogeneous catalyst for the reduction of aromatic nitro
compounds.231
Another interesting supporting material was identified by
Mitsudome et al., who prepared hydrotalcite (HT)-supported
Cu NPs. The material was synthesized by mixing HT with an
aqueous solution of copper(II) trifluoromethanesulfonate,
adding aqueous ammonia to adjust the pH to 8.0, and stirring
the resulting mixture at rt for 1 h. The HT-supported Cu(II)
nanomaterial obtained in this way was used to catalyze the
oxidant-free dehydrogenation of alcohols.211
3.2.3. Polymer-Supported Cu NPs. Although polymer-
supported NPs could in principle be regarded as a subclass of
NPs supported on carbon-based materials, they have been
developed to an extent that warrants separate discussion.278−280
Kang and co-workers prepared Cu NPs on cellulose acetate
polymer by reducing Cu(II) complexes with hydrogen gas in
the presence of cellulose acetate to obtain supported Cu2O and
Cu NPs with particle sizes ranging from 30 to 120 nm.193
Dendrimer-encapsulated Cu NPs were prepared by chemical
reduction of Cu complexes trapped in dendrimers using sodium
borohydride (NaBH4).232 Yang and co-workers reported a
facile procedure for the preparation of Pd−Cu NPs supported
on one-dimensional hybrid nanofibers using hydrated bacterial
cellulose nanofibers (BCFs) as templates.281 The material was
prepared by immersing the BCFs in an aqueous solution of
PdCl2 and CuCl2, after which the metallic ions adsorbed on the
BCFs were reduced with potassium borohydride to provide the
BCF-supported metallic Pd−Cu NPs.
Yuan’s group reported the synthesis of Cu NPs supported on
nitrogen-rich copolymeric microsheets233 that were prepared by
the incomplete condensation of melamine and cyanuric
chloride. The polymeric microsheets were then suspended in
a solution of copper(II) acetate and sonicated for 1 h. The
composite was then treated with hydrazine hydrate to produce
the desired materials. The nitrogen dopants in the material
enhanced its interaction with Cu, allowing the microsheets to
act as good support materials.
Pham et al. prepared composite polymer-supported Cu NPs
by mixing ∼50 nm Cu NPs with poly(3,4-(ethylenedioxy)-
thiophene)/poly(styrenesulfonate) (PEDOT/PSS).234 The Cu
NPs were synthesized by reducing copper salts with hydrazine
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Table 3. Literature Procedures for Preparing Well-Defined Alloyed Cu Nanomaterials and Multimetallic NPs with Cu or Cu-
Based NPs

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Table 3. continued

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Table 3. continued
in the presence of the surfactant cetyltrimethylammonium
bromide (CTAB) and stabilizer poly(vinylpyrrolidone) (PVP).
3.2.4. Silica- or Silicon-Supported Cu NPs. Silica- and
silicon-supported nanomaterials have been used extensively in
fields ranging from catalysis to adsorption and optics, among
others.189,282,283 Silica supports offer surface silanols that can
facilitate NP binding, while silicon has unique electronic and
optical properties that can enable the preparation of
sophisticated multifunctional hybrid materials.
Mesoporous silica has emerged as an ideal supporting
material for many types of NPs because of its controllable pore
size and shape as well as its large surface area. Various
mesoporous silica materials, including SBA-15,235,236,239,242,284
MCM-41,216 MCM-48,285 and KIT-6,240 have been used to
support Cu NPs. For example, Moreno-Piraján and co-workers
prepared Cu nanocatalysts confined in SBA-15 via an in situ
reduction process.235 A more sophisticated method based on
MW irradiation was used to synthesize Cu NPs supported on
ZnO/SBA-15.284 Gutierrez et al. have reported the reduction of
copper chloride in the presence of mesoporous silica support
MCM-41 to yield MCM-41-supported Cu NPs. 216 A
combination of wet impregnation and organometallic chemical
vapor deposition (OMCVD) was also successfully used to
deposit Cu NPs with tailored particle sizes onto a mesoporous
silica KIT-6 matrix at loadings of 3−7 wt %.240
Silicon-supported Cu NPs have been synthesized in a variety
of ways. Kang and co-workers prepared Cu NPs supported on
silicon nanowires (SiNWs) by immersing the SiNWs into an
aqueous CuSO4 solution,241 causing the initially yellow SiNWs
to gradually become ashy as the Cu NPs were deposited. Fellahi
et al. reported a similar synthesis in which SiNWs were dipped
into an aqueous solution of CuCl2 (0.035 M) and HF (1.45 M)
for 1 min at ambient temperature.237 The resulting material was
rinsed with water and dried under a nitrogen flow to afford the
final Cu-NP-grafted materials.
3.2.5. Zeolite-Supported Cu NPs. Because of its unique
and interesting porous morphology, zeolite has been widely
used as a support for metal NPs for different applications,
including catalysis and adsorption.286−289 In most cases, the
final nanomaterials were prepared by exchanging Cu ions for
the zeolites’ native cations and then reducing them with
external reducing agents. For example, Petranovskii et al.
prepared Cu catalysts supported on natural zeolites with
different structures using an ion-exchange procedure247 in
which natural zeolites were ion-exchanged in an aqueous
solution of Cu salts for 72 h at ambient temperature and then
reduced under a hydrogen gas flow for 4 h at temperatures of
423−723 K. The steric hindrance imposed by the zeolite cages
controls the size of the resulting Cu nanoclusters, and the
limited pore diameter increases the catalytic selectivity. In a
related work, Cu NPs supported on NaY zeolite were
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Review
synthesized by stirring a mixture of zeolite and Cu(NO3)2·
3H2O at 363 K for 12 h to induce cation exchange.246 The
cation-exchanged zeolites were activated at 723 K for about 6 h
and then treated with hydrazine hydrate in an ethanolic
solution to generate Cu NPs within the zeolite. This process
was easily monitored by visual inspection because it caused the
material’s color to change from light green to dark brown.
Harnos et al. have also synthesized Cu and Cu2In NPs
supported on amorphized zeolites by conventional aqueous ion
exchange, followed by reduction.290
3.3. Other Cu-Based NPs
Cu has often been employed as a component of alloys and
multimetallic nanosystems. While the synthetic strategies used
to prepare such nanomaterials are generally similar to the
methods discussed in the preceding sections, we have chosen to
discuss them separately because of the unique thermal,
electrical, and catalytic properties exhibited by these more
complex multimetallic materials. Table 3 collates the literature
survey covering the preparation of such systems with details of
the synthetic strategy deployed in each case.
A representative example of Cu-based nanoalloy formation is
the synthesis of Cu1.5Mn1.5O reported by Fan and co-
workers.313 In their procedure, Cu2CO3(OH)2 and MnCO3
are mixed in a molar ratio of 1:2 with a 20% stoichiometric
excess of H2C2O4·2H2O and then loaded into a plastic vial with
agate milling balls, followed by grinding at 600 rpm under
ambient conditions for 2 h (Figure 10). The ground material is
then calcined in air to afford the final product.
Lu et al. have synthesized CuInSe2 NPs with a water-in-oil
microemulsion-mediated process.304 As described earlier, the
reverse micelles in the W/O microemulsion system serve as
nanoreactors that restrict the growth of the NPs. In another
example, Cheng and co-workers reported the hydrothermal
synthesis of ultrasmall delafossite CuCrO2 nanocrystals.310 The
resulting material was thermally stable at temperatures up to
400 °C. Hashimoto and co-workers synthesized rhombohedral-
like CuFeO2 crystals via a hydrothermal method in which
propionaldehyde serves as a reducing agent for Fe(NO3)3·
9H2O and Cu(NO3)2·3H2O.297
Another class of materials in this category is nanosized
bimetallic Cu species. Ploehn and co-workers used dendrimer−
metal nanocomposites as precursors in the preparation of silica-
supported monometallic Pt, Cu, and bimetallic Pt−Cu
catalysts.322 After impregnation of the dendrimer−metal
nanocomposites, the catalysts were thermally treated and
then activated.322 Similar ceria-supported Pd−Cu and Pt−Cu
bimetallic catalysts have been synthesized by wet impregnation
of metal salts in an aqueous solution,323 while Nitani and co-
workers reported a more erudite radiolytic method that uses a
4.8 MeV electron beam to reduce aqueous ions and has
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successfully been employed in the synthesis of bimetallic Pt−
Cu composite NPs supported on γ-Fe2O3.324
3.4. Growth Mechanisms of Cu NPs
An understanding of the mechanisms by which NPs form and
grow is important for the development of their synthetic
methods. NP growth and the size and shape of the products are
mainly controlled by the properties of the precursor and the
reaction conditions. Unfortunately, despite many experiments
and computational studies, the exact mechanisms involved in
these processes are still not entirely clear yet. The following
sections summarize results that have shed light on the growth
of Cu and Cu-based NPs to provide a broad overview of the
field and its complexities.
3.4.1. Growth of Cu NPs. The mechanisms underlying the
growth of Cu NPs are affected by the synthetic strategies
adopted for their preparation. Perhaps the most common
mechanism is so-called “seed”-mediated growth, which can
occur in the presence of external reducing agents and/or under
other reducing conditions which induce NP formation. For
example, Liu et al. reported the preparation of Cu nanorods via
seed-mediated growth in solution with PVP as a surface
stabilizer and soft template.325 The Cu NPs acted as “seeds” of
nucleation sites for nanorod growth and PVP as a soft rodlike
template in a dilute solution. Wiley and co-workers reported
the synthesis of Cu nanowires via the reaction between
Cu(NO3)2 and hydrazine in the presence of aqueous NaOH
and ethylenediamine.326 The Cu nanowires are grown from
spherical seeds, as seen in SEM images of the products taken at
different times over the course of the reaction.
Ikeda et al. have synthesized Cu NPs from an ion-doped
polyimide precursor via a mechanism that is proposed to
involve in situ reduction (Figure 11).327 The growth of Cu NPs
is assumed to occur in accordance with the Ostwald ripening
process (i.e., “the smaller NPs sacrifice themselves to make the
larger NPs in order to decrease surface-to-bulk ratios” 327). Cu
atoms or clusters that dissociate from the surfaces of smaller
particles can be entrapped in the polyimide matrix, after which
they can diffuse into the bulk phase of the matrix to enable
further NP growth. This process has been described as
“diffusion-controlled aggregative growth of Cu NPs”.327
́
Dominguez-Vera has reported the synthesis of Cu NPs inside
an apoferritin matrix together with a possible mechanism for
their growth (Figure 12).328 To begin with, some of the Cu2+
ions penetrate through the hydrophilic channels and form small
clusters of copper(II) oxide/hydroxide in the apoferritin cavity
due to the collection of octahedrally oxygen-coordinated
Cu(II) ions. These small Cu(II) clusters are then transformed
into metallic Cu via NaBH4 reduction which subsequently
aggregate, leaving Cu NPs trapped inside the cavity.328
A different growth mechanism was reported by Liu et al., on
the basis of their studies. Cu vapor generated by one-step
synthetic method and is then redeposited on a substrate under
vacuum or at very low pressures to form Cu nanostructures.329
It was found that the Cu vapor could easily be deposited
(undergoing nucleation) and grown into rods at relatively low
temperatures, on supports such as amorphous carbon films or
molybdenum grids. The resulting Cu nanorods and nanowires
are crystalline and almost defect-free. It was suggested that the
most favorable sites for Cu nucleation are the rough edges of
the holes in the carbon film, indicating the importance of rough
carbon for Cu vapor renucleation.
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Review
In a unique electrochemical synthesis of Cu nanomaterials,
Lin and co-workers demonstrated the pyramidal growth of Cu
NPs on a gold substrate during electrodeposition.330 A
mechanism was proposed whereby Cu atoms were electro-
deposited epitaxially onto the (111) surface of the gold
substrate to form the first (111) plane of the pyramidal crystals
(Figure 13a). The sodium salt of dodecylbenzenesulfonic acid
(DBSA) was then adsorbed onto the surface of the deposited
Cu. Although it played no role in the electrochemical process,
this adsorption caused further electrodeposition of Cu on the
(100) facets. This is mainly because the capping agent DBSA
interacts more strongly with the atoms on the (111) facets than
with those of the (100) facets.330,331 The shapes of the Cu
nanocrystals depended on the ratio of DBSA to Cu2+,
presumably due to the differences in the adsorption of the
surfactant/polymer onto specific Cu surfaces (Figure 13b).
When the ratio of DBSA to Cu2+ was decreased from 3:1 to 2:1,
cubic Cu NPs were obtained due to the difference in growth
rates between the (111) and (100) directions.330 On the other
hand, multipodal Cu materials were obtained when PVP was
used instead of DBSA.330,332 Zhong and co-workers have
reported that the preferential adsorption of capping agents on
the nanocrystal planes can affect the growth rates of various
crystal facets, leading to differently shaped nanocrystals.58 In
another study, Sarkar et al. observed the growth of Cu
nanocrystals with diverse shapes on thin polypyrrole films after
electrochemical deposition from a CuSO4 solution under both
potentiostatic (constant-potential) and galvanostatic (constant-
current) conditions.333 When the current was constant, Cu
nanostructures with distinct shapes such as nanowires,
microwires, fractals, and cubes were obtained. However, only
fractal and cubic Cu nanocrystals were observed after
electrodeposition with under- or over-peak potentials. It was
postulated that the Cu nanoparticles grew according to the
Volmer−Weber (i.e., instantaneous) nucleation mechanism.
A mechanism for the formation of Cu NPs induced by laser
ablation in liquids was recently proposed by Madhavi and co-
workers.133 The pulsed laser beam initially ablates the target
Figure 10. Soft reactive grinding process using dry precursors for the
preparation of copper−manganese mixed oxide catalysts. Reprinted
with permission from ref 313. Copyright 2007 Springer Science +
Business Media, LLC.
material, which expands in the liquid environment to generate a
range of different species, including NPs, small clusters, free
atoms, and ions. The desired NPs may be formed by the rapid
condensation of molten globules, collisions between plume
species, or the nucleation of small clusters from free atoms.
Direct nucleation of Cu from the condensed plume continued
during subsequent stages, offering growing centers for incoming
species.133
Gedanken and co-workers prepared Cu NPs by a
sonochemical method334 using a reduction process involving
radical species originating from water molecules under the
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Figure 11. Proposed mechanism of Cu NP formation via in situ reduction of an ion-doped polyimide precursor.

influence of ultrasound: H2O ))))) H• + OH•. The resulting proposed: Cu(citrate) − (aq) + C 5 H 11 O 5 −CHO(aq) →
H• radicals efficiently reduced Cu2+ to metallic Cu NPs (Cu2+ + Cu2O(s) + C5H11O5COOH(aq).
2H• → Cu0 + 2H+; nCu0 → (Cu0)n (aggregates)). Some Cu2O The formation of these differently shaped crystals under
was also observed due to the partial oxidation of metallic Cu by specific conditions was mainly attributed to differences in the
the hydrogen peroxide byproduct formed from water: Cu0 + ratio of the growth rates along the (100) and (111) plane
H2O2 → Cu2O + H2O. However, when the experiment was directions.337 PVP can be used as a stabilizing additive to
performed under an atmosphere of argon and hydrogen, only prevent the aggregation of these nanomaterials, and can also
pure Cu NPs were obtained, presumably because the hydrogen control the shape of the resulting nanocrystals: as the
could consume OH• so the reducing environment was concentration of PVP was increased, the nanocrystals went
preserved and there was no possibility of further oxidation.334 from cubes to truncated octahedra, octahedra, and finally
3.4.2. Growth of CuOx NPs. The growth mechanisms of spheres (Figure 15). The formation of star-shaped Cu2O
copper oxide nanomaterials are heavily dependent on the particles is depicted in Figure 16, which shows that smaller NPs
specific processes used for their synthesis. Pan and co-workers could be transformed into smaller nanooctahedra followed by
reported the preparation of CuO nanoneedles by thermal Ostwald ripening to generate larger particles. At the solution’s
oxidation of a pure Cu nanocrystalline layer in the presence of low supersaturation limit, the (100) plane was relatively
unstable, so growth along the (100) direction became
air.335 The nanoneedles’ growth was suggested to be controlled
by the diffusion of Cu ions from the substrate due to the local
electrical field generated by oxygen ions at the solid/gas
interface. Subsequently, as the temperature increased, the Cu2O
phase formed, and this intermediate species, Cu2O, served as a
catalyst, allowing the inner Cu and O atoms to diffuse and
produce the CuO nanoneedles. This sequence of events was
described as a “self-catalyzed base-up diffusion process”.335 In
another study, Hsiegh et al. observed the formation of well-
ordered CuO nanofibers via a self-catalytic growth mechanism
(Figure 14).336 Nanosized Cu nuclei were uniformly distributed
on a Cu substrate by applying a high-voltage input to a CuSO4
solution. While ion diffusion was reported to be the rate-
determining step in this process, the distribution of the Cu2+
ions was controlled in a way that caused them to accumulate
uniformly in the nanochannels of a polycarbonate template.
This caused the spherical Cu nuclei to react with oxygen to
form CuO nanofibers via a self-growth process presumably
serving as autocatalysts.336
Sui et al. have synthesized Cu2O nanocrystals with various Figure 12. Structure of apoferritin and schematic representation of the
shapes (including cubes, truncated octahedra, octahedra, and preparation of CuII− and Cu0−apoferritin NPs. Reprinted with
nanospheres) by reducing a copper citrate solution with permission from ref 328. Copyright 2008 Wiley-VCH Verlag GmbH &
glucose.337 A stoichiometric reduction process has been Co. KGaA.

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energetically favorable. As a result, well-defined star-shaped
Cu2O structures with symmetrical horns were produced.337
3.4.3. Growth of Other Cu-Based NPs. Because of their
distinct growth mechanisms, this section discusses the growth
of Cu NPs encapsulated in different materials such as those
recently reported by Wang et al., who prepared Cu NPs
encapsulated in multilayer graphene via chemical vapor
deposition (CVD) of Cu(acac)2 at 600 °C. They proposed a
coalescence model to explain the generation of these Cu/
graphene core/shell structures (Figure 17).338 First, gaseous
Cu(acac)2 was generated at 150 °C, which was moved to a
higher temperature part of the furnace with the help of the
carrier gas H2. Second, the Cu(acac)2 decomposed to produce
small carbon/Cu nanoclusters. Third, carbon/Cu nanoagglom-
erates were formed due to collisions in the reaction mixture.
Finally, the Cu/graphene core/shell NPs were prepared by the
coalescence of Cu atoms into Cu nanocores along with
subsequent diffusion of the carbon atoms out onto the
nanocores’ surfaces, where they coalesced into the graphene
layer.338 The formation of these nanomaterials was enabled by
the rapid interdiffusion of Cu and C atoms at the reaction
temperature and the extremely low solubility of C in Cu.339
Figure 13. (a) Proposed growth of pyramid-shaped Cu NPs. (b)
Proposed growth of variously shaped Cu NPs under different
conditions. Reprinted with permission from ref 330. Copyright 2009
Springer Science + Business Media, LLC.
Figure 14. Self-catalytic growth mechanism for CuO nanofiber arrays from Cu nuclei. Reprinted with permission from ref 336. Copyright 2003 AIP
Publishing LLC.
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Review
3.5. Characterization
Many commonly used materials characterization techniques can
be applied to Cu and Cu-based NPs to elucidate their
composition, morphology, and other physicochemical proper-
ties. While a detailed discussion of such techniques is beyond
the scope of this review, a brief overview covering the most
important and widely used techniques is warranted.
Scanning electron microscopy (SEM) and transmission
electron microscopy (TEM) are two major methods that can
be used to determine the morphology and detailed structures of
many nanomaterials, including Cu and related nanosystems.
Rapid progress in electron microscopy has resulted in the
development of ancillary techniques such as energy-dispersive
X-ray spectroscopy (EDS), high-resolution transmission
electron microscopy (HRTEM), high-angle annular dark-field
scanning transmission electron microscopy (HAADF-STEM),
scanning tunneling microscopy (STM), and elemental
mapping, etc. These methods have been routinely applied to
characterize nanomaterials not only in terms of their texture but
also with respect to their composition, their attachment to
supporting materials, etc.
X-ray diffraction (XRD) is another invaluable technique that
enables elucidation of the structure of a crystal as well as the
extent of its crystallinity. This method has been used
extensively to determine lattice parameters for Cu NPs and
related substances. Although XPS (X-ray photoelectron spec-
troscopy) is primarily a surface characterization technique, it
has also been used to determine the elemental composition of
surfaces and to investigate the chemical and electronic states of
individual elements in specific surfaces. In this particular
context, XPS can be used to establish the presence of Cu or Cu-
based NPs in a sample, and to determine the oxidation states of
their copper centers as well as their potential attachments.
Possibly the most popular method for determining the
amount of Cu present in a given nanomaterial is atomic
absorption spectroscopy (AAS).240 Because metal nanostruc-
tures have unique electronic features, UV−vis spectroscopy has
become another useful method for their characterization. For
instance, the representative bands of CuO in the 250−350 and
600−800 nm regions are attributed to Cu2+−O− charge-
transfer transitions and d−d transitions of dispersed CuO
species, respectively.240,340 Moreover, because Cu NP is a
surface-enhanced Raman spectroscopy (SERS)-active material,
the SERS technique has been used to provide useful
information about the size and shape of Cu NPs. For example,
surface plasmon peaks at wavelengths of 380 and 600 nm were
observed in a study on Cu nanowires.130 In addition to the
aforementioned techniques, gas adsorption/desorption experi-
ments are often used to acquire information about the specific
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surface areas of nanomaterials and to determine their pore
volumes and pore sizes. Such information is particularly
important for characterizing porous Cu-based nanostructures
or porous support materials for Cu NPs, and for correlating
their structure with their catalytic activity.
4. CATALYTIC APPLICATIONS OF Cu NPs IN ORGANIC
TRANSFORMATIONS
Copper-based nanoparticles have been used as catalysts for a
very wide range of organic transformations. They are
particularly attractive for this purpose because they often
enable reactions to be conducted under green or sustainable
reaction conditions that would reduce the activity of conven-
tional catalysts. This section describes the Cu-NP-mediated
catalysis of click chemistry, reduction and oxidation reactions,
A3 coupling, cross-coupling, tandem and multicomponent
reactions, C−H functionalization, clock reactions, borylation,
oxidative coupling, and other miscellaneous reac-
tions.29,49,301,341−346 Although the discussion is primarily
focused on catalytic applications, the synthesis of the catalytic
nanomaterials is also detailed where relevant.
4.1. Azide−Alkyne Cycloaddition via Click Chemistry
The Huisgen 1,3-dipolar cycloaddition reaction between azides
and terminal alkynes is possibly the most well-known “click”
reaction and has made a lasting imprint on industrial, biological,
and synthetic chemistry.347,348 This reaction provides syntheti-
cally and biologically useful 1,2,3-triazole-type products with
high regioselectivity under ambient conditions. It proceeds
smoothly in the presence of air and water and tolerates a wide
range of functional groups.349,350 Cu and Cu-based NPs have
been widely used to catalyze Huisgen 1,3-dipolar cycloaddition
reactions of azides, including a one-pot hydrazinolysis/Dimroth
rearrangement catalyzed by ligand-free Cu NPs.351−354
Borah et al. have reported the preparation of Cu NPs
embedded in nanoporous modified montmorillonite355 pre-
pared by treating montmorillonite with H2SO4. The confine-
ment of the Cu NPs in the nanopores limits their growth,
restricting their diameter to around 10 nm. The material was
shown to efficiently catalyze the 1,3-dipolar cycloaddition of
aliphatic azides with terminal alkynes in water at room
temperature (Figure 18). The process is compatible with
Figure 15. Effects of different PVP concentrations on the morphology
of Cu2O nanocrystals, prepared by reduction using glucose. Reprinted
from ref 337. Copyright 2010 American Chemical Society.
both linear and branched azides, including the hindered 1-
azidoadamantane. However, recyclability experiments showed
that the catalyst’s efficiency decreased slightly during repeat
runs, and that this decrease correlated with a progressive
decrease in its specific surface area from 299 m2/g (for the fresh
catalyst) to 227 m2/g (after the fourth recycle). At the same
time, the pore diameter of the montmorillonite increased from
4 to 8 nm, and a small amount of CuO was observed.
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The high reactivity of Cu NPs was exploited by Yus and co-
workers to catalyze the cyclization of azides with terminal
alkynes.356 Cu NPs were easily prepared by the spontaneous
reduction of CuCl2 with lithium metal and 4,4′-di-tert-
butylbiphenyl in THF at room temperature. TEM micrographs
demonstrated that these conditions furnished well-defined
spherical NPs with a narrow size range (ca. 3.0 ± 1.5 nm).
These NPs exhibited high activity in the 1,3-dipolar cyclo-
addition of azides and alkynes in THF at 65 °C with Et3N as a
base, efficiently promoting the coupling of aromatic, benzylic,
allylic, and aliphatic azides and aromatic and aliphatic terminal
alkynes to provide an array of triazoles in high yields (Figure
19). Unfortunately, the Cu NPs were not recyclable because
they were prepared as “homogeneous” suspensions in THF,
highlighting the need for supported equivalents.
Cu NPs immobilized on robust supports such as charcoal
(Cu NPs/C) were prepared by Alonso et al. and similarly
shown to catalyze the multicomponent synthesis of 1,2,3-
triazoles.357 Several supports for the Cu NPs were evaluated,
including silica, metal oxides, and carbon materials, but only the
charcoal-supported Cu NPs/C proved to be a robust and active
heterogeneous catalyst that gave high yields for the multi-
component reaction depicted while also showing excellent
recyclability.357
Extensive characterization of Cu NPs/C revealed the
presence of spherical NPs with diameters of 6 ± 2 nm in an
oxidized state (that is to say, they consisted of Cu2O and CuO).
The use of these nanoparticles as catalysts for a three-
component sequential process involving azide formation and
1,3-dipolar cycloaddition (Figure 20) was investigated thor-
oughly. Organic azides can be prepared and generated in situ by
the reaction of sodium azide with organic halides or
arenediazonium salts, which can be catalyzed by Cu. The Cu
NP/C catalyst exhibited excellent stability upon recycling over
five catalytic runs, and the leaching of Cu into the solvent was
negligible (the Cu content of the solvent was determined to be
below 50 ppb), making it possible to obtain organic products
without copper contamination after just a simple filtration.
Yus and co-workers also reported another Cu-NP/C-
catalyzed multicomponent reaction involving a domino
azidolysis of epoxides and 1,3-dipolar cycloaddition of alkynes
in water at 70 °C.249 While the 1,3-dipolar cycloaddition step
regioselectively formed 1,4-adducts, the outcome of the epoxide
azidolysis depended on the steric and electronic properties of
the epoxide. Briefly, the azide anion attacked the less hindered
carbon of monoalkyl-substituted oxiranes, but the opposite
behavior was observed with monoaryl-substituted oxiranes,
while vinyl epoxides reacted via an SN2′ pathway (Figure 21).
Recycling experiments conducted on a model reaction revealed
a progressive decrease of the isolated yield upon reuse, from
98% for the first run to 70% after the fourth run. This
decreasing activity was not attributed to a loss of Cu to the
solvent by solubilization because inductively coupled plasma
mass spectrometry (ICP-MS) measurements indicated only
very low levels of metal contamination (<80 ppb) in the
residual reaction mixture after the first and second uses of the
catalyst. Importantly, screening experiments using conventional
Cu catalysts, including Cu, CuO, Cu2O, CuCl, and CuCl2,
demonstrated the superiority of Cu NPs/C for the multi-
component process. The superior performance of the nano-
catalyst was attributed to its large surface-to-volume ratio and
its distribution on the support.
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Figure 16. Shape evolution of Cu2O crystals prepared by glucose reduction as a function of the reaction time. Reprinted from ref 337. Copyright
2010 American Chemical Society.
Figure 17. Schematic of the experimental setup used to prepare Cu/
graphene core/shell NPs and the proposed growth model for their
formation. Reprinted with permission from ref 338. Copyright 2012
Elsevier Ltd.
Lately, magnetic nanocatalysts have attracted a lot of
attention because of their easy recovery using an external
magnet.358−360 The deposition of Cu NPs onto commercially
available silica-coated maghemite NPs (MagSilica, 5−30 nm)
yielded a magnetically recoverable and active nanocatalyst for
chemical transformations involving terminal alkynes.361 The
catalyst was conveniently prepared by adding MagSilica to a
suspension of Cu NPs synthesized by reducing CuCl2 with Li
and DTBB (4,4′-di-tert-butylbiphenyl) in THF at room
temperature. The product’s temperature-programmed reduc-
tion profile indicated that the Cu it contained was mainly
present in the form of CuO, suggesting that the Cu NPs are
oxidized during handling of the catalyst under air. TEM
experiments revealed spherical NPs with an average size of 3.0
± 0.8 nm and a loading of 6.8 wt % on the support. This
nanocatalyst was evaluated for its ability to catalyze the
multicomponent process involving sequential organic azide
formation and 1,3-dipolar cycloaddition with terminal alkynes
at 70 °C (Figure 22).
In a related example, copper nitride (Cu3N) NPs supported
on superparamagnetic silica microspheres (Cu3N/Fe3N@SiO2)
have been employed for the synthesis of 1,2,3-triazoles.362
Their synthesis was based on earlier work pertaining to the
fabrication of core/shell CoFe2O4@SiO2 microspheres (Figure
23).363
The initial step of the catalyst’s synthesis produced silica
particles with mesoporous shells impregnated with iron nitride
phases having Fe3N as a major component. These shells were
designated Fe3N@SiO2 and were used as a support material for
Cu to afford Cu3N/Fe3N@SiO2, which was prepared by
embedding a Cu source into the Fe3N@SiO2 microspheres and
then annealing them at 250 °C in NH3. TEM images of Cu3N/
Fe3N@SiO2 reveal a core/shell structure with a shell thickness
of approximately 100 nm surrounding a dense silica core
(Figure 24 a, b). The surface morphology of the silica template
was preserved during the growth of the Fe3N and Cu3N phases,
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suggesting that both nitride phases are successfully incorpo-
rated into the pores inside the shells without affecting the
morphology of the parent core/shell materials.
The Cu3N/Fe3N@SiO2 catalyst was employed for the
synthesis of 1,2,3-triazoles from a variety of alkynes and azides.
All reactions progressed rapidly in the presence of tertiary
amines with good to excellent yields and high selectivity
(Figure 25). Extensive solvent screening experiments identified
acetonitrile as the optimal solvent for this protocol.362
Song and co-workers have reported the preparation of ZnO/
CuO core/branch hybrid NPs by controlled oxidation of
copper deposited on ZnO nanospheres.364 The core/branch
hybrids were prepared by reducing a Cu precursor on
Figure 18. Cu-NP/montmorillonite-catalyzed 1,3-dipolar cycloaddi-
tion of aliphatic azides with terminal alkynes in an aqueous medium.
polycrystalline ZnO spheres to obtain ZnO/Cu2O hybrid
NPs (Figure 26a), which were then subjected to controlled
oxidation, leading to the formation of CuO branches on the
ZnO surface (Figures 26b−d). This material represents an
unusual bifunctional catalyst with a branched morphology in a
colloidal metal oxide system. Due to their high surface area and
the many active facets of the CuO branches, these NPs
exhibited remarkable catalytic activity in [3 + 2] azide−alkyne
cycloaddition reactions under sonication together with good
stability and reusability (Figure 27). The ability to combine
different metal oxide supports and NPs offers the prospect of
producing a wide range of selective and eco-friendly catalysts
with potential energy-related applications.
Cuprous oxide (Cu2O) rhombic octahedra, dodecahedra, and
cubes exhibiting highly facet-dependent (HFD) catalytic
activity have been employed for the synthesis of 1,2,3-
triazoles,365 often in water and at room temperature.366,367
Notably, these facet-dependent Cu2O nanomaterials reportedly
have better catalytic activity than irregularly shaped and PVP-
coated Cu2O NPs, clearly demonstrating the potential of HFD
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Cu2O oxides in catalysis. Figure 28a−c shows SEM images of
the rhombic octahedral, dodecahedral, and cubic Cu2O
nanostructures, which are a few hundred nanometers in size.
Figure 19. Cu-NP-catalyzed cycloaddition of azides and terminal
alkynes.
Whereas the octahedra and cubes had relatively wide size
distributions, the rhombic dodecahedra were more uniformly
sized. All of the NPs have sharp faces that strongly affect their
catalytic activity. Figure 28d−i shows crystal models of the
(100), (110), and (111) planes of HFD Cu2O.368
Attempts to use these Cu2O nanocrystals as catalysts for the
synthesis of 1,4-disubstituted 1,2,3-triazoles revealed that
rhombic dodecahedral Cu2O {110} facets were more active
than octahedral Cu2O {111} facets, and that both of these
structures were always more active than nanocubes (Table 4).
The rhombic dodecahedra were used in a synthesis of the
antiepileptic drug rufinamide, demonstrating their potential in
the heterogeneous catalysis of industrially relevant reactions.
Recently, a one-step synthetic method involving polymer-
ization between olefin-decorated ionic liquids and vinyl-
functionalized magnetic nanoparticles (MNP@MPS) was
reported for the synthesis of the nanocatalyst MNP@ImAc
(immobilized metal affinity chromatography)/Cu (Figure
29).369
The embedded Cu(II) species were well characterized and
shown to catalyze multicomponent click reactions among
Figure 20. 1,3-Dipolar cycloadditions catalyzed by Cu NPs/C.
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alkyne, inorganic azides, and organic halides in the presence of
aqueous sodium ascorbate to produce triazole derivatives
(Figure 30). The catalyst was recyclable until the fifth cycle;
however, a longer reaction time was needed afterward,
presumably due to the loss of catalysts during the magnetic
separation. More than 30 examples with different combinations
of reactants confirmed the excellent substrate scope and the
versatility of the reaction.
Khan and co-workers reported the preparation of mono-,
bis-, and tristriazole derivatives using CuO NPs and sodium
ascorbate as catalysts and 10,10-dipropargyl-9-anthrone as a
primary building block in water.370 The green synthetic
Figure 21. Tandem epoxide azidolysis/1,3-dipolar alkyne cyclo-
addition catalyzed by Cu NPs/C in water.
protocol, recyclability, and functional group tolerance make
this process attractive, and it could potentially be used for the
synthesis of supramolecular architectures.
In a similar fashion, aqueous azide−alkyne click reactions
catalyzed by magnetic bimetallic Cu−iron NPs have been
reported,371 where the iron(0) core provides an important
handle for magnetic recyclability. Recyclable Cu nanocatalysts
were also shown to be capable of catalyzing the synthesis of
1,2,3-triazoles in aqueous media.372 Another benign synthesis in
water has shown that charcoal-supported Cu NPs could be
employed for catalytic synthesis of 1,2,3-triazole derivatives,191
and numerous protocols exist for achieving azide−alkyne
cycloadditions with various Cu nanocatalysts under sustainable
conditions.345,373−380
4.2. Coupling Reactions
Coupling reactions such as homocouplings, Heck and
Sonogashira reactions, and C−S, C−O, C−B, and C−Se
couplings are some of the most common and important
reactions in modern organic chemistry.264,381−388 Various
noble- and transition-metal catalysts have been developed and
employed for these reactions. Cu and Cu-based NPs in
particular have emerged as reliable, cost-effective, “drop-in”
options for many reported catalytic protocols, and it has been
shown that their adoption can increase the sustainability of such
processes.382
A recent report described the homocoupling of terminal
alkynes using MW-induced nanotube (MINT)-supported Cu
NPs389self-assembled tubular silica-based nanostructures that
enclose and support Cu NPs. XPS analysis revealed that these
materials contain both Cu(0) and Cu(II) species in a 3:2 ratio.
When this nanocatalyst was stirred in neat phenylacetylene with
1,4-diazabicyclo[2.2.2]octane (DABCO) as a base under MW
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Figure 22. Sequential organic azide formation and 1,3-dipolar
cycloaddition catalyzed by Cu NPs on MagSilica.
irradiation, the homocoupled diyne was obtained in a yield of
75% within 30 min, along with various enyne side products.
The dimerization of terminal alkynes by Cu NPs, under
oxidant-, ligand-, and Pd-free conditions, was reported by
Radivoy and co-workers.390 Cu NPs were generated in situ
from anhydrous CuCl2 and DTBB using lithium metal as the
Figure 23. Synthesis of a Cu3N/Fe3N@SiO2 silica microsphere. Dark
blue spheres and green ovals represent Fe3N and Cu3N NPs
embedded within the mesoporous shells of a silica sphere, respectively.
Reprinted with permission from ref 362. Copyright 2010 Royal Society
of Chemistry.
reducing agent in THF. The homocoupling proceeded in
refluxing THF with good to excellent yields, with both aliphatic
and aromatic alkynes (Figure 31). For aliphatic alkynes, the
addition of Na2CO3 improved the reaction rate and allowed the
use of substoichiometric amounts of Cu NPs (50 mol %),
whereas a large excess of metal (400 mol %) was required with
aromatic alkynes.
The Heck reaction, one of the most important C−C-bond-
forming reactions generally catalyzed by palladium-based
catalysts, is widely used in the synthesis of various
pharmaceuticals.391,392 However, given the low abundance
and high cost of Pd, additional efforts have been devoted to find
a cost-effective approach for such reactions either by
eliminating or by minimizing the use of expensive noble
metals/ligands. A greener approach was developed by
Nasrollahzadeh and co-workers for the preparation of Pd/
CuO nanocomposites from Theobroma cacao L. seed extract,
and the materials have been utilized for the phosphine-free
Heck coupling reaction and for the 4-nitrophenol reduction
(Figure 32).393 The proposed mechanism for the synthesis of
the nanomaterials involved reduction of metal precursors (Mn+)
by flavonoid (FlOH)-based species (Figure 33). The
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Figure 24. High-resolution TEM images of Cu3N/Fe3N@SiO2 at low
and high magnifications (a, b). Elemental distribution maps of (c) Fe
and (d) Cu in Cu3N/Fe3N@SiO2. Reprinted with permission from ref
362. Copyright 2010 Royal Society of Chemistry.
Figure 25. Synthesis of various 1,2,3-triazoles mediated by Cu3N/
Fe3N@SiO2.
phosphine-free Heck coupling showed high to excellent yields
of the products with good functional group tolerance. The
catalyst was recyclable up to the sixth cycle without any loss of
activity.
The Suzuki−Miyaura reaction is a well-known Pd-catalyzed
procedure for C−C bond formation and is extensively used,
especially for the synthesis of biphenyls.394,395 Rothenberg and
co-workers have reported the use of Cu-based nanoclusters as
substitutes for Pd catalysts.396 Fifteen different cluster
combinations of four metals (Cu, Pd, Ru, and Pt) were
prepared by reducing mixed metal chlorides with tetraocty-
lammonium formate (TOAF) in DMF. The catalytic activity of
the resulting nanocolloid catalysts, whose particle sizes ranged
from 1.6 to 2.1 nm, were then evaluated using as a test reaction
the coupling of iodobenzene with phenylboronic acid in the
presence of K2CO3 as a base in DMF at 110 °C (Table 5).
While Pd exhibited the greatest activity of the monometallic
catalysts, bi- and trimetallic composites of Cu/Pd and CuPd/
Ru, respectively, were remarkably active. Further studies
showed that cross-couplings using both Cu/Pd and Cu/Pd/
Ru gave better conversions than Pd alone for aryl bromides, but
low conversions for aryl chlorides.
A bimetallic system of Pd−CuO NPs in hollow silicalite-1
single crystals (Pd−CuO@Hol S-1) was prepared using the
“impregnation−dissolution−recrystallization” process by Dai et
al.397 This binary-metal (oxide) nanomaterial (encapsulated
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Figure 26. TEM images of (a) ZnO/Cu2O core/shell hybrid NPs and
(b) ZnO/CuO core/branch NPs. (c) HAADF-STEM image and
(inset) elemental mapping of Zn (red) and Cu (green) for a single
ZnO/CuO core/branch NP. (d) XRD spectra of ZnO/Cu2O and
ZnO/CuO hybrid NPs. The bars represent (a, b) 200 nm and (c) 50
nm. Reprinted with permission from ref 364. Copyright 2012 Royal
Society of Chemistry.
Figure 27. [3 + 2] azide−alkyne cycloaddition reactions catalyzed by
the ZnO−CuO hybrid nanocatalysts under ultrasonic irradiation.
within silicalite-1 single crystals) has been employed as a
catalyst in Suzuki−Miyaura coupling, showing superior catalyst
activity as compared with the encapsulated single-Pd catalyst.
The high catalytic activity of the former has been attributed to
the higher dispersion of the catalytic species due to the
presence of copper oxide in the material (Figure 34).
The core/shell nanomaterial Cu2O@Cu, which has a Cu2O
core and a Cu shell, was tested as a catalyst for the Sonogashira
coupling by Varma and co-workers.398 The nanomaterial is
constructed using a simple protocol whereby the porous Cu-
outside Cu2O@Cu is assembled in an inside-out fashion
(Figure 35). The core/shell nanoparticles successfully catalyzed
the coupling of various aryl iodides and phenylacetylenes to
yield the corresponding diarylalkynes in excellent yields (85−
94%) without the need for any sort of ligand or noble metal
(Pd) (Figure 36). It is important to note that no desired
products were observed when only Cu2O or Cu was employed.
Thus, porous Cu2O@Cu may be a good substitute for
expensive Pd and other noble-metal catalysts that are widely
used to promote the Sonogashira coupling reaction. The
Cu2O@Cu NPs recovered after the reaction retained their
core/shell structure and were thus stable. The catalysts could be
recycled without any loss of activity, demonstrating that they
are compatible with cost-effective and environmentally benign
syntheses.
The Sonogashira coupling reactions for the synthesis of
ynones, have garnered interest due to their potential for the
development of valuable organic compounds/intermedi-
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ates.399−401 In this respect, replacement of conventional Pd-
based catalytic systems by earth-abundant metal-based catalysts
still remains an area of active research. Bhanage and co-workers
have reported a Cu/Cu2O nanocatalyst for the synthesis of
ynone derivatives via Sonogashira coupling between acyl
chlorides and terminal alkynes;104 the catalyst was synthesized
via a ligand- and template-free, MW-assisted method using
Cu(OAc)2·H2O as the precursor in 1,3-propanediol. The
coupling reaction between phenylacetylene and benzoyl
chloride offered the highest conversion and yield under an
inert atmosphere, when toluene and triethylamine were used as
the solvent and base, respectively. Diverse substituents on both
the reactants have been explored to afford good to excellent
yields of the respective ynone products (Figure 37). However,
no evidence of recyclability of the nanocatalysts was provided.
Kim et al. have reported that Cu NPs catalyze the cross-
coupling of alkyl bromides or chlorides with organomagnesium
reagents.402 Commercially available Cu NPs (10 mol %) were
used as catalysts with 1-phenylpropyne as an additive in THF at
room temperature, and excellent results were obtained for an
array of substrates. Initial optimization studies revealed that
40−60 nm Cu NPs gave higher yields than smaller NPs (5−7
nm). Primary, secondary, tertiary, and even phenyl Grignard
reagents could be coupled to primary alkyl bromides and
chlorides in high yields using this protocol (Figure 38).
However, coupling of phenylmagnesium chloride required a
higher loading of Cu NPs (20 mol %) to obtain an acceptably
high yield of the desired products. Interestingly, the method
was compatible with a number of functional groups, including
acetals, alkenes, amides, secondary alkyl bromides, and even
esters and free alcoholic functionalities. Mechanistic studies
revealed that the cross-coupling occurred mainly through an
SN2 mechanism, although a minor radical pathway was also
observed.
Graphite-supported copper oxide NPs (CuO NPs/Gr)
efficiently promoted the C−H arylation of benzoquinones in
water with arenediazonium salts generated in situ.263 The CuO
NP/Gr catalyst was prepared from a mixture of Cu(OAc)2 and
graphite in MeOH under a hydrogen atmosphere. TEM
analysis revealed the formation of spherical NPs that were
homogeneously dispersed on the support with an average
diameter of 3.1 nm. XPS analysis revealed the Cu 2p3/2 peak at
934.0 eV and the satellite shakeup near 938−946 eV
characteristic of Cu2+ species. The absence of peaks associated
with metallic Cu and Cu+ indicated that Cu2+ was the only Cu
species on the graphite. Optimization studies demonstrated the
graphite’s importance for catalytic activity: an alternative
charcoal-supported CuO NP catalyst exhibited lower reaction
yields. The reaction’s scope was explored with anilines bearing
diverse substituents, including halogens, nitriles, ketones, esters,
and even alkynes (Figure 39). Naphthoquinone substrates can
be used instead of benzoquinone without reducing the
reaction’s efficiency provided that dimethyl sulfoxide
(DMSO) is added as a cosolvent to improve the solubility of
the reactants, and CaCO3 is used to buffer the solution. The
CuO NP/Gr catalyst exhibited good recycling properties on at
least five consecutive reuses with only a very slow erosion of the
reaction yields.
Single Cu NPs of about 2 nm generated by reducing CuCl2
in refluxing DMF under ligand- and surfactant-free conditions
were very active in the Ullmann O-arylation of aryl halides with
phenols.403 Characterization of the Cu NPs revealed them to
predominantly contain low oxidation state Cu species, most
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Figure 28. SEM images of (a) cubic, (b) octahedral, and (c) rhombic dodecahedral Cu2O nanocrystals. The scale bars represent a distance of 1 μm.
Crystal structure models of cuprite (Cu2O) showing the (d, e) {100}, (f, g) {111}, and (h, i) {110} surfaces. Oxygen atoms are shown in dark gray,
while Cu atoms are shown in white. In panel e, the uppermost layers of oxygen atoms have been removed to clearly show the number of surface Cu
atoms. Panel g shows the {111} planes rotated 63° with respect to the model shown in panel f. The triangle in panel g encloses the same area as that
shown in panel f. The cubic unit cell parameter is a. Reprinted with permission from ref 365. Copyright 2013 Wiley-VCH Verlag GmbH & Co.
KGaA.

Table 4. Comparison of the Catalytic Activity of Different
Cu2O Nanocrystals in 1,3-Dipolar Cycloaddition Reactionsa
a Graphene has been used as a robust support for Cu NPs that
Reaction conditions: 1 (0.25 mmol), 2 (0.25 mmol), and NaN3 (0.38
mmol) in EtOH (3 mL) at 55 °C. RD = rhombic dodecahedra, and
OC = octahedra. Yields are those of the isolated products.
likely covered by a thin oxide layer. This unsupported
nanomaterial promoted the coupling of aryl bromides and
iodides with electron-rich phenols at low catalyst loadings (0.01
mol %), but iodoheteroarenes were unsuitable substrates
(Figure 40). Unfortunately, recycling experiments showed
3748
that the catalyst was strongly deactivated during or after the
reaction: the yields obtained in the second and third runs of the
coupling of iodobenzene with 3,5-dimethylphenol were 51%
and 18%, respectively.
Zareyee and co-workers utilized the high cation-exchange
capacity of clinoptilolite (CP) to impregnate KF into the
structure, and the ensuing solid base (KF/CP) was used in
conjunction with CuO nanocatalysts for C−O coupling.404
With the reaction various substrates could be converted to aryl
ethers with moderate to excellent yields. Apart from the
conventional oxidative addition, followed by a reductive
elimination mechanism, the authors proposed the involvement
of F− as a proton scavenger, thereby making the resulting K+−
phenolate more nucleophilic (Figure 41).
catalyze the O- and N-arylation of aryl halides. This
nanomaterial was prepared by the simultaneous reduction of
copper acetate and graphene oxide (GO) using hydrazine.188
GO was obtained by chemical exfoliation of graphite following
a modification of Hummer’s method. TEM analysis showed the
presence of small Cu NPs with sizes of 2−3 nm on the
graphene surface. A mixture of Cu oxidation statesCu(0),
Cu(I), and Cu(II)was detected by XPS analysis. This
nanocatalyst was evaluated for the arylation of phenols and
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Figure 29. Synthesis of the MNP@ImAc/Cu catalyst. Reprinted with permission from ref 369. Copyright 2015 Royal Society of Chemistry.
Figure 30. Huisgen 1,3-dipolar cycloaddition, catalyzed by MNP@
ImAc/Cu.
Figure 31. Homocoupling reaction catalyzed by Cu NPs.
N-heterocycles with aryl halides, which proceeded well with a
variety of aryl iodides, bromides, and even chlorides bearing
both electron-donating and electron-withdrawing substituents
(Figure 42). Phenols bearing electron-donating groups that
enhanced their nucleophilicity exhibited particularly high
reactivity.
The same catalysts have been used to promote the N-
arylation of imidazole, pyrazole, pyrrole, and benzimidazole
with aryl iodides and electron-deficient aryl bromides. The
graphene-supported Cu NPs exhibited good activity in these
reactions in DMSO at 100 °C with Cs2CO3 as the base (Figure
43).
Interestingly, the use of arylboronic acids instead of aryl
halides allowed the arylation to proceed under milder
conditions (at 40 °C) in MeOH without any external base
(Figure 44). Boronic acids bearing electron-withdrawing groups
and sterically hindered ortho-substituted boronic acids were
3749
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Figure 32. Green synthesis of Pd/CuO NPs using an extract of cocoa
seeds as the reductant (NZV = nano-zerovalent, and FlOH =
flavonoid). Reprinted with permission from ref 393. Copyright 2015
Elsevier Ltd.
Figure 33. Heck reaction catalyzed by Pd/CuO NPs.
both good arylating agents but required longer reaction times
(∼12 h). The reaction’s scope was remarkably broad, and high
yields were obtained irrespective of the nature of the partners,
which included imidazole, pyrazole, benzimidazole, phthali-
mide, succinimide, benzamide, and sulfonamides. Recycling
experiments revealed the robustness of the catalyst, which could
be reused more than seven times without exhibiting any
appreciable declines in yield.
The C−N cross-coupling reaction was achieved by deploying
CuO NPs/SiO2 as a nanocatalyst,405 and the versatility was
demonstrated using a diverse set of aryl halides and secondary
amines in the presence of KOH as a base in DMSO at 120 °C
(Figure 45). Because of the absence of kinetic conversion data
for different reactions, the actual comparison of products was
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Table 5. Suzuki Cross-Coupling Reactions Catalyzed by
Nanostructured Pd and Multimetallic Composites
Figure 34. Suzuki−Miyaura coupling catalyzed by (Pd−CuO@Hol S-
1).
Figure 35. SEM images of inside-out core/shell architectures (Cu2O@
Cu). Reprinted with permission from ref 398. Copyright 2012 Royal
Society of Chemistry.
rather difficult. On the basis of the isolated yield, however, it
was discerned that the substituent effect was more pronounced
in the case of aryl bromides as compared to aryl iodides; aryl
chlorides were also chosen because of their easy availability and
comparable activity. Using the reaction, a diverse number of
secondary amines, including dialkylamines, secondary aryl-
amines, N-heterocyclic compounds, and primary arylamines,
could be coupled with various aryl halides within a relatively
short time (minimum 7 min to maximum 3 h), affording the
respective coupled products in good to excellent yield. The
catalyst was shown to be recyclable (five times) without losing
its activity.
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Figure 36. Sonogashira coupling reactions of aryl iodides with
phenylacetylenes.
Figure 37. Sonogashira coupling reaction between acyl chlorides and
terminal alkynes using Cu/Cu2O as a nanocatalyst.
Functionalized multiwalled carbon nanotubes (MWCNTs)
have been decorated with CuO NPs and were used as an
efficient heterogeneous catalyst for the N-arylation of
imidazole.406 The nanocatalyst was prepared by oxidizing
MWCNTs in a mixture of HNO3 and H2SO4, followed by a
mechanical mixing of the solid product with Cu(OAc)2.
Calcination at 350 °C then furnished the CuO NP/MWCNT
catalyst with a Cu loading of 7.60 wt % (Figure 46).
The morphology of the MWCNTs was determined by TEM
at various magnifications (Figure 47). The images clearly
Figure 38. Cu-NP-catalyzed cross-coupling reactions of alkyl bromides
and chlorides with organomagnesium reagents.
showed that the external walls of the MWCNTs were decorated
with numerous very small and well-dispersed CuO NPs. A
histogram of the CuO NPs’ sizes (Figure 47b, inset) showed
that they have a fairly wide size distribution, ranging from 10 to
26 nm in diameter.
XPS analysis confirmed the formation of Cu2+ species with
no evidence for the presence of Cu0/Cu+ species. Optimization
studies revealed the superiority of N,N-dimethylacetamide
(DMAc) as a solvent compared to toluene, DMF, and DMSO.
The influence of the base was also investigated, revealing that
arylation proceeded efficiently when K2CO3 was used but not
with KOH, K3PO4, or t-BuOK. Reactions involving electron-
deficient bromo- and chloroarenes in the presence of 1 mol %
catalyst at 120 °C for 24 h were particularly successful (Figure
48). Interestingly, the particle size strongly influenced the
reaction outcome: catalysts with 60−80 nm CuO NPs
displayed markedly lower catalytic activity. The CuO NP/
MWCNT catalyst exhibited excellent reusability over up to
eight recycles, with only marginal discernible deactivation.
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Francisco and Radivoy407 prepared Cu NPs on an inert
magnetically reusable maghemite−silica support by mixing the
support with a freshly prepared suspension of Cu NPs obtained
by reducing anhydrous CuCl2 with lithium sand and DTBB.
The resulting maghemite−silica−Cu nanomaterial was a viable
catalyst for the N-(hetero)arylation of imidazole with (hetero)-
aryl bromides and iodides (Figure 49). It is worth noting that
Figure 39. C−H arylation of benzoquinones catalyzed by graphite-
supported copper oxide NPs.
the maghemite−silica−Cu was readily removed from the
reaction mixture with an external magnet, and could be reused
in up to three reaction cycles without losing its activity or
undergoing any observable leaching of Cu.
Zhou and co-workers have reported the use of a copper
amino acid-grafted graphene hybrid material (A−G−Cu) for
the catalysis of N-arylation,189 which is the most important and
useful reaction for C−N coupling products (Figure 50).
Similarly, Fernández-Merino et al. have synthesized graphene
and silver−graphene hybrids with natural bioreductants such as
pyridoxamine, pyridoxine, and vitamin B2, in addition to the
amino acids arginine, histidine, and tryptophan.408 These
workers focused on amino acid-grafted graphene (A−G) as a
support because amino acids coordinate strongly to metal
ions409 and can enhance the catalytic activity of metal NPs on a
supporting material. The distribution and loading of Cu NPs in
these hybrid nanomaterials could be adjusted by changing the
identity of the grafted amino acid. Most of the A−G−Cu
materials catalyzed the N-arylation of imidazole with
iodobenzene in excellent yield (90%), whereas only 66%
yield was obtained when Cu grafted on graphene (G-Cu) was
used. The excellent activity of A−G−Cu can thus be attributed
to the combination of Cu NPs with amino acid-grafted
graphene.
CuO nanoparticles have been employed as efficient
heterogeneous catalysts for N-arylation of indoles (Figure
51)410 wherein the nanocatalysts were synthesized by an
3751
Review
Figure 40. Ullmann O-arylation of aryl halides with phenols.
electrospun method using copper acetate and a poly(vinyl
alcohol) (PVA) polymer.410 In the presence of 2,2′-bidentate
ligands (1,10-phenanthroline or 2,2′-bipyridine), a base
(KOH), and CuO nanocatalysts, the arylation of indoles with
Figure 41. CuO-NP-catalyzed C−O coupling reactions.
different aryl halides was investigated. The catalysts showed
excellent recyclability up to the fourth cycle without any
leaching of the Cu species as exemplified with reaction between
indole and 4-bromotoluene. This new promising technique
allowing the generation of CuO NPs may be deployed in the
future for the development of nanocatalysts.
In a recent example, Movahed et al. reported the synthesis of
Cu@Cu2O NPs supported on RGO (reduced graphene oxide)
and its use as an efficient nanocatalyst for the N-arylation of N-
heterocycles.195 The catalyst was prepared from a basic solution
containing GO and CuSO4 in one step where L-ascorbic acid
served as a reducing agent. The highest yield (98%) and
conversion (100%) were obtained within 1 h at 110 °C in the
presence of Cu@Cu2O NPs/RGO when used in DMSO with
Cs2CO3 as a base. This optimized reaction condition was then
applied for the N-arylation of various N-heterocycles, and the
reaction gave moderate to excellent yields of the N-arylated
products (Figure 52). The catalyst was also easily recycled,
giving yields ranging from 92% to 83% from the first to fourth
cycle, respectively. The leaching tests of Cu species, as
performed by the hot-filtration step, followed by AAS analysis,
showed that the amount of copper species increased on going
from the first to the fourth cycle (from 0.9% to 1.4%),
presumably because of weaker interaction of Cu@Cu2O with
the RGO surface.
Bakr and co-workers have synthesized branched copper
hydroxide and copper oxide nanocages as thioetherification
catalysts.70 The sizes of the cores of the nanocages and the
lengths of the branches could be controlled by varying the
quantity of surfactant and the temperature during the synthesis
of the nanocages. The length of the branches varied from 85 to
232 nm, and the cores were between 19 and 240 nm in
diameter. TEM micrographs of a single branched Cu(OH)2
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Figure 42. Arylation of phenols with aryl halides catalyzed by Cu NPs
on graphene.
Figure 43. Arylation of N-heterocycles with aryl halides catalyzed by
Cu NPs on graphene.
Figure 44. Arylation of N-heterocycles with arylboronic acids
catalyzed by Cu NPs on graphene.
nanocage showing its morphology and branches at different
reaction times are shown in Figure 53. The branched CuO
nanocages were used to promote the cross-coupling of
alkanethiols and aryl iodides at 130 °C under MW irradiation
in dimethyl sulfoxide with cesium carbonate as a base. The
coupling product was obtained in good yield in the catalyst’s
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Review
Figure 45. C−N cross-coupling catalyzed by CuO NPs/SiO2.
presence (91%); without the catalyst, the yield was only 3%
(Figure 54).
Carbon−sulfur heterocoupling is an important organic
transformation and a vital step in the preparation of numerous
biological and pharmacological products.411 The MW-assisted
coupling of thiophenols with aryl halides to form diaryl
thioethers using a magnetically recoverable heterogeneous Cu
catalyst has been described by Baig and Varma.412 The
magnetic catalyst was prepared in two steps by sonicating
nanomagnetite with dopamine hydrochloride, followed by the
addition of CuCl and its reduction into Cu NPs with
NaBH4.412 The resulting nanoparticles were spherical with
diameters of 10−25 nm, and the Cu content of the magnetite
was determined to be 0.82% by inductively coupled plasma
atomic emission spectroscopy (ICP-AES). Extensive optimiza-
tion studies showed that the coupling was best conducted in
environmentally benign i-PrOH as the solvent under MW
irradiation at 120 °C. Both aryl iodides and aryl bromides were
coupled to thiophenols in short reaction times (25−30 min) in
very high yields (85−98%) (Figure 55). It should be mentioned
that the nanocatalyst was easily recoverable with an external
magnet and reused in three consecutive runs on a model
reaction without any appreciable loss of efficiency. ICP-AES
analysis of the reused catalyst showed that its content of Cu did
not change after recycling.
Trivedi et al. investigated the catalytic activity of CuO NPs,
prepared via the thermal treatment of {[Cu 4 (CN) 5 -
(C5H5N)4]}n polymer, to perform C−N, C−O, and C−S
coupling reactions (Figure 56).413 The precursor polymer
{[Cu4(CN)5(C5H5N)4]}n was synthesized using pyridine on
ammoniacal CuCN in a solvent combination of dichloro-
methane and methanol (1:1, v/v) at ambient temperature. The
nanocatalyst showed good functional group tolerance for all the
reactions, and no leaching was observed during the course of
the reactions. On the basis of the fact that electron-withdrawing
substituents reacted faster in all the reactions, the proposed
mechanism possibly involves oxidative addition, followed by a
reductive elimination process.413 Recently, Sharma et al. also
reported maghemite-supported Cu NPs for C−O, C−N, and
C−S coupling reactions under mild conditions.414
The synthesis of S-aryl- and S-vinyldithiocarbamates in water
via a one-pot three-component reaction between an aryl halide,
carbon disulfide, and a secondary amine was accomplished
using spherical Cu NPs (2−6 nm) in an unidentified oxidation
state.415 The experimental protocol is simple, requiring no
added base or additives and using refluxing water as the only
solvent (Figure 57). The reaction worked well with aryl iodides
and vinyl bromides, and with amines, including dimethylamine,
diethylamine, piperidine, pyrrolidine, and morpholine. When
using vinyl bromides, the reaction proved to be highly
stereoselective with both (E)- and (Z)-isomers. These studies
revealed the high catalytic activity of Cu NPs compared to
metallic Cu and spherical Cu NPs.
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Figure 46. Preparation of the CuO NP/MWCNT catalyst. Reprinted with permission from ref 406. Copyright 2013 Elsevier.

Figure 49. N-(Hetero)arylation of imidazole catalyzed by Cu NPs on

magnetically recoverable silica. Left: TEM image of maghemite−
silica−Cu showing maghemite, silica, and Cu NPs. Right: Reusability
profile of the Cu/MagSilica catalyst. Reprinted with permission from
Figure 47. TEM images of (a) pure MWCNTs and (b, c) CuO/ ref 407. Copyright 2013 Elsevier.
MWCNTs (the inset in (b) shows the size distribution of CuO NPs).
Panels d−f show high-resolution TEM images of CuO/MWCNTs.
Reprinted with permission from ref 406. Copyright 2013 Elsevier.

Figure 50. Synthesis of A−G−Cu hybrids and their use in the N-

arylation of imidazole with iodobenzene. Reprinted from ref 189.
Copyright 2013 American Chemical Society.

and related compounds can generally be obtained by coupling

Figure 48. N-Arylation of imidazole catalyzed by CuO NPs on aryl iodides with phenyl selenol, the benzene selenoate anion,
MWCNTs. or diphenyl selenide in the presence of Cu(I) and Ni(II)
catalysts,418,419 although some of these protocols require
Yavari et al. have demonstrated a multicomponent C−S multistep procedures and necessitate the handling of unstable
arylation reaction catalyzed by CuO NPs. The catalysts were reagents.
prepared by heating aqueous Cu(OAc)2·2H2O at 100 °C for 1 Unsupported Cu NPs with an average diameter of 4.3 ± 0.6
h, followed by washing with water and ethanol.416 The nm prepared by reducing copper sulfate with hydrazine in
reactions between malononitrile, carbon disulfide (CS2), and ethylene glycol were used for the phenylselenylation of aryl
various aryl halides were investigated using the catalyst (Figure
58). Both electron-withdrawing and electron-donating sub-
stituents on the aryl halide were found to work reasonably well,
giving moderate to good yields of the final products. Moreover,
among the halides, the iodide reacted faster as compared to
their bromide counterparts.
Organoselenium compounds are important in biological and
pharmaceutical applications due to their antitumor, antimicro-
bial, antioxidant, and antiviral properties.417 Diaryl selenides Figure 51. N-Arylation of indole catalyzed by CuO NPs.

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Chemical Reviews
iodides and vinyl bromides in water.420 The oxidation state of
the Cu nanocatalyst was not reported, rendering comparisons
with other Cu nanocatalysts quite difficult. The phenyl-
selenylation proceeded in high yields with Zn dust (3 equiv)
as an additive in refluxing water, using a high loading of Cu NPs
(20 mol %). The reaction with (E)-vinyl bromides was perfectly
stereoselective, but the same was not true for (Z)-vinyl
bromides (Figure 59). The catalyst gradually deactivated upon
successive reuses, probably because of the agglomeration of Cu
NPs, which increased its crystallite size from 4 nm for the
freshly prepared catalyst to 40 nm after the first cycle.
Commercially available CuO NPs (mean size 33 nm) have
been successfully used for the MW-assisted synthesis of
diselenides, ditellurides, and disulfides,421 and the superiority
of CuO NPs over bulk CuO, CuI, and nano-CuFe2O4 was
clearly demonstrated. The synthesis of organoyl dichalcoge-
nides was carried out in DMSO, with KOH as a base, under
MW irradiation at 80 °C (Figure 60); the reactions efficiently
furnished diselenides with short reaction times (7−15 min)
regardless of whether the aryl iodide carried electron-donating
or electron-withdrawing groups. However, alkyl iodides gave
lower yields. The formation of disulfides and ditellurides was
Figure 52. N-Arylations of N-heterocycles using Cu@Cu2O NPs/
RGO as a nanocatalyst.
less efficient, and lower yields of the corresponding
dichalcogenides were usually observed. Although recycling
experiments were not reported, the authors noticed that CuO
NPs agglomerated to a significant extent after the first catalytic
run, which is likely to compromise the reuse of the catalyst.
Rao and co-workers have reported the cross-coupling of
diaryl diselenides and aryl halides using CuO NPs without any
added ligand in DMSO.422 Under these conditions, a variety of
aryl selenides were synthesized in good to excellent yields from
readily available diaryl diselenides and aryl halides (Figure 61).
The substrate scope of this coupling reaction of diphenyl
diselenide was explored using various substituted aryl halides.
The desired products were obtained efficiently when using aryl
iodides bearing electron-withdrawing substituents. However,
this protocol did not work for the coupling of aliphatic
dimethyl diselenides with aryl halides.
In addition to C−S, C−Se, and C−N coupling, commercially
available Cu NPs have been used to borylate primary and
secondary alkyl bromides with bis(pinacolato)diboron in the
absence of phosphines at room temperature.423 It was noted
that Cu NPs exhibited excellent activity with a variety of
substrates, delivering good to excellent yields of the desired
3754
Review
Figure 53. (A) Bright-field (BF) TEM micrograph of a branched
Cu(OH)2 nanocage. (B) A single Cu(OH)2 nanostructure showing
the branches extending from the core. (C) Tomogram of (B) showing
the stacked structure of the branches, which run straight through the
material and stack in an alternating fashion. (D) BF-TEM micrograph
after 12 h. (E) BF-TEM micrograph of a nanocage containing both
CuO and Cu2O obtained after a 14 day reaction time. Reprinted from
ref 70. Copyright 2014 American Chemical Society.
products (Figure 62) in the borylation of deactivated primary
and secondary alkyl bromides with organodiboron compounds.
A mechanistic study was conducted using the borylation of
cyclopropylmethyl bromide mediated by Cu NPs as a model
reaction. The only product obtained was 3-butenylboronate, in
a yield of 40%; there was no evidence of the simple boryl
substitution product (Figure 62). The exclusive isolation of the
ring-opened product suggests that the Cu-NP-catalyzed
reaction proceeds via a radical mechanism, in contrast to the
conclusion drawn for the Cu-NP-catalyzed coupling of
Grignard reagents.402
γ-Lactams and related motifs are important components of
various biologically active compounds, natural products, and
pharmaceuticals,424−428 and therefore, several effective method-
ologies for preparing a wide variety of γ-lactams, including α-,
β-, and γ-substituted ones, have been reported.429−439 The
development of efficient C−H bond functionalization reactions
that proceed under benign conditions is a major goal of current
research in organic chemistry, and studies along these lines have
borne impressive fruit.440−444 Synthetic protocols allowing the
cleavage of C−H bonds adjacent to nitrogen atoms under
oxidative conditions in the presence of catalysts have been
reported.445 For instance, Kantam and co-workers found that
CuO NPs catalyzed the formation of N-aryl-γ-amino-γ-lactams
via the oxidative coupling of aromatic amines with 2-
pyrrolidinone (Figure 63).446 This CuO-NP-catalyzed protocol
was compatible with a broad range of substrates, offering good
to excellent yields and regioselectivity in each case. In addition,
the reaction is compatible with various functional groups,
including −CF3, −COOEt, −COMe, −COOH, −NO2, and
halides. Finally, nitrogenous heteroarenes such as pyrazole and
indole successfully coupled with 2-pyrrolidinone/N-methyl-2-
pyrrolidone (NMP) in a dual C−H activation process,
providing a remarkably atom-efficient method for forming
C−C bonds adjacent to the nitrogen atom in lactams.
The oxidative coupling of heterocyclic secondary amines
such as indole, pyrazole, and benzimidazole with 2-
pyrrolidinone/NMP has also been investigated. Indole and
pyrazole underwent C−H activation rather than N−H
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Figure 54. Left: Growth mechanisms of branched Cu(OH)2 and copper oxide NPs. Right: Catalytic thioetherification of benzyl iodide over time in
the presence and absence of branched CuO nanocages formed by a 20 h reaction with 10 equiv of PVP at room temperature. Reprinted from ref 70.
Copyright 2014 American Chemical Society.

Figure 55. Synthesis of thiophenols catalyzed by a magnetite−Cu

nanocatalyst.

activation to provide 5-(1H-indol-3-yl)pyrrolidin-2-one, 5-(1H-

indol-3-yl)-1-methylpyrrolidin-2-one, and 1-methyl-5- (1H-
pyrazol-1-yl)pyrrolidin-2-one in moderate to good yields
(Figure 64).446
4.3. Reduction Reactions
Reduction plays a central role in the chemical industry;
reductive processes are used extensively in the synthesis of
dyes, biologically active compounds, active pharmaceutical
ingredients, and rubber chemicals, among others.447−451
Nanostructured Cu-catalyzed hydrogenation reactions have
gained prominence because the catalysts could potentially be
much less expensive than noble metals; selective and efficient
protocols that proceed under sustainable conditions with
copper nanoparticle catalysis have been identified for a wide
range of hydrogenation reactions.50,452−456 The hydrogenation
of olefins to the corresponding saturated hydrocarbons is one
of the most important organic transformations, and is typically
achieved using transition-metal catalysts such as Pd, Pt, Rh, Ni,
or Cu in the presence of reducing agents such as molecular
hydrogen, hydrazine, or formate.453
Garcia and co-workers have reported the synthesis of Cu
NPs supported on diamond NPs (DH) annealed with
hydrogen (Cu/DH) and their catalytic performance in the
reduction of olefins with hydrazine hydrate as a reducing
3755
Figure 56. CuO-catalyzed C−N coupling (a, b), C−O coupling (c),
and C−S coupling (d) reactions.
agent.186 The catalytic activity of Cu/DH in the reduction of
styrene to ethylbenzene was compared to that of Au/DH and
Pd/DH; Cu/DH was found to have a higher initial reaction
rate and final conversion level than the other two catalysts. In
all cases the selectivity for ethylbenzene was more than 99%.
The higher activity of the Cu/DH catalysts could be attributed
to their ability to promote diimide formation (Figure 65).457,458
The catalysts’ efficiency and stability were assessed by
performing the reduction on a large scale (50 mmol); under
these conditions, the reduction of styrene to ethylbenzene was
completed in 130 h with a catalyst turnover number (TON) of
30 617 cycles.
The substrate scope of the optimized reduction protocol
using Cu/DH was explored with a range of styrenes, all of
which were reduced with very good selectivity (Figure 66).186
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Figure 57. One-pot three-component synthesis of S-aryl- and S-
vinyldithiocarbamates in water catalyzed by Cu NPs.
Figure 58. Multicomponent C−S arylation reaction catalyzed by CuO
NPs.
Various methods for using CO2 (carbon dioxide) as a
reactant are currently being explored, with the aim of using this
cheap and abundant material as a feedstock for the synthesis of
useful products and synthetic fuels while also mitigating CO2
emissions.459 At present, one of the most viable methods for
converting CO 2 into a feedstock appears to be its
thermocatalytic hydrogenation (CO2 + 3H2 → CH3OH +
Figure 59. Phenylselenylation of aryl iodides and vinyl bromides in
water catalyzed by unsupported Cu NPs.
H2O). This reaction is favored because methanol is a valuable
commodity chemical and could serve as a synthetic fuel if it
were produced in large quantities.
Natesakhawat has investigated the active sites and structure−
activity relationships of Cu-based nanocatalysts supported on
ZnO and ZrO2 for methanol synthesis from a stoichiometric
mixture of CO2 and H2.460 An array of catalysts (CuO, ZnO,
CrZr, CuZn, CuZnZr, CuZnZrY, and CuZnZrGaY) were
synthesized using a reverse coprecipitation method.460,461 XPS
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Review
experiments showed that metallic Cu was present on the
surfaces of both reduced and spent catalysts, and there was no
Figure 60. Synthesis of organoyl dichalcogenides catalyzed by CuO
NPs.
evidence of monovalent Cu+ species in the materials.460 The
fact that similar results were obtained for six related materials
with different metal oxide additives, different Cu particle sizes,
and varying degrees of ZnO crystallinity supports the
conclusion that metallic Cu is the active material in methanol
synthesis catalysts. Small Cu particles gave higher TOF values
in methanol synthesis, confirming the structure sensitivity of
this reaction. Although the catalytic activity and Cu surface area
are strongly associated, a relationship between TOF and Cu
microstrain could not be established. The integration of Ga2O3
and Y2O3 into CuZnZr catalysts enhances the dispersion and
reducibility of the Cu, conferring superior methanol synthesis
activity.
Figure 61. Cross-coupling reaction between iodobenzene and
diphenyl diselenide catalyzed by CuO NPs.
Cu NPs have been employed as catalysts for the reduction of
a series of aromatic nitro compounds to the corresponding
amino products with sodium borohydride, giving aromatic
amino compounds in high yields.462 The catalyst could be
recycled for several reaction cycles. A variety of aromatic nitro
compounds were investigated for the reaction (Figure 67); the
best yields were obtained using 10 mol % Cu NPs in THF/
water (1:2).
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In another example, silicon nanowire array (SiNWA)-
supported Cu NPs were synthesized by a simple galvanic
displacement reaction, and the resulting nanowires were used in
the catalytic reduction of 4-nitrophenol to 4-aminophenol with
sodium borohydride (NaBH4) in an aqueous solution.463 The
Figure 62. Cu NP-catalyzed borylation of alkyl bromides with an
organodiboron compound.
catalytic activity of the nanowires was found to be comparable
to that of SiNWA-supported noble-metal (Ag and Au) NPs.
These silicon nanowires exhibited excellent dispersion,
providing stabilization for nanosized metal NPs while offering
a high surface to volume ratio and many catalytically active
sites.464,465 Cu NPs supported on silicon nanowire arrays
performed very well in the catalytic conversion of 4-nitrophenol
to 4-aminophenol (Figure 68).
In a typical reduction, the 4-nitrophenol accepts an electron
from the donor BH4− after the adsorption of both onto the NP
surface. This is followed by a series of electron-transfer steps
leading to the final products, which then desorb form the NP
surface. SiNWAs/Cu could be reused and recycled for five
consecutive cycles, achieving conversions of more than 95%
each time. Additional catalytic applications include the
degradation of organic dyes such as methylene blue (MB)
and rhodamine B (RhB). SiNWAs/Cu is therefore considered
to have good prospects as an efficient, cost-effective, and benign
reusable catalyst that could potentially replace some noble
metals in various catalytic processes.
Zboril and co-workers have reported the preparation of Cu
NPs via the reduction of Cu ions with sodium borohydride and
sodium polyacrylate.466 The as-synthesized Cu NPs with an
average diameter of 14 nm were produced via aggregation and
coalescence of the predominantly formed ultrasmall nano-
particles (3 nm). Furthermore, the synthesis of Cu2O
nanotubes with an average size of 18 nm was also achieved
by controlled aeration of the “as-synthesized” Cu NPs, which
were employed for the borohydride reduction of 4-nitrophenol
in an aqueous medium. The catalytic performance of both Cu
and Cu2O NPs was comparable to that of other noble-metal-
based nanocatalysts (Ag, Au, Pd, and Pt).466 Water-dispersible
poly(acrylic acid) (PAA)-capped Cu NPs have been employed
for the catalytic reduction of 4-nitrophenol to 4-aminophenol at
room temperature in reactions that were followed by UV−vis
spectroscopy.467 Their catalytic efficacy was found to be
extraordinarily high with no evidence of self-oxidation of the
PAA.
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Figure 63. CuO-NP-catalyzed oxidative coupling of amines with 2-
pyrrolidinone.
Cu NPs supported on a zeolite framework have been utilized
for the reduction of C−C multiple bonds and carbonyl
compounds using 2-propanol as a hydrogen donor that can be
easily removed from the reaction system.246 These stable NPs
in a zeolite framework were recyclable with good catalytic
activity in the absence of a base, and it was concluded that this
selective and efficient hydrogenation catalyst could potentially
replace some common heterogeneous olefin hydrogenation
catalysts468,469 and homogeneous olefin hydrogenation catalysts
based on Ni,468,470 Fe,471 Pd,472,473 and Pt474 which are
sometimes problematic to use in view of their high cost and
difficulty of handling/separation. The reduction of aromatic
carbonyl compounds could also be achieved using this catalyst;
smooth transformations were achieved in each case, affording
the corresponding alcohols in good to excellent yields (Figure
69). The generality of the reaction was established for the
reduction of carbon−carbon multiple bonds, and CC double
bonds in all of the selected examples were easily hydrogenated
at 70 °C (Figure 70).
Ethanol is an eco-friendly alternative fuel for fuel cells whose
adoption has been spurred by the depletion of readily accessible
fossil fuel reserves.475−477 It is mainly manufactured via the
fermentation of sugars or by ethylene hydration, but the
bioprocesses involved in ethanol production from biomass are
costly.478−480 Ethanol can also be obtained from syngas via the
hydrogenation of dimethyl oxalate (DMO) (Figure 71), which
can thus bridge the gap between the nonrenewable petroleum
route and expensive biofermentation with minimum waste,
cost, and energy depletion.481 Syngas can be synthesized from a
variety of materials, including fossil fuels (e.g., natural gas, coal,
and naphtha) and organic wastes.482,483
Zhu et al. have designed a bifunctional Cu-NP-decorated
mesoporous Al2O3 catalyst for highly efficient ethanol syn-
thesis.41 The catalyst was prepared via a spatial restriction
strategy by immobilizing the Cu NPs on mesoporous Al2O3.
The synthetic approach avoided sintering problems, yielding a
material that was stable at 270 °C for more than 200 h. Due to
the catalyst’s high number of pores and precisely assembled
Cu−acid sites, the desired product, ethanol, was obtained from
DMO in excellent yield (∼94.9%).
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Figure 64. Dual C−H activation of indole and pyrazole with 2-pyrrolidinone or NMP.

Figure 65. Proposed mechanism for the Cu/DH-catalyzed reduction

of styrene.

Figure 66. Reduction of various olefins catalyzed by Cu/DH.

The synthesis of ethanol by DMO hydrogenation involves Figure 67. Cu-NP-catalyzed reduction of aromatic nitro compounds.
the hydrogenation of CO bonds and subsequent cleavage of
C−O bonds in ethylene glycol (EG) (Figure 71). 41 recycling catalysts difficult. Various nanomaterials have been
Interestingly, the catalysts’ intrinsic activity increased as the designed to catalyze organic oxidation reactions, including Pd,
size of the Cu NPs decreased; this could be due to a number of Pt, Cu, Co, Ru, and Rh,490,491 but with very few exceptions,
factors, including the wide-ranging effects of textural morphol- these catalysts include noble metals, and require the use of
ogy, the electronic properties of the Cu NPs and Cu−Al2O3 expensive ligands.
interfacial sites, and the equilibrium of surface Cu0−Cu+ Among the many known oxidation reactions, the catalytic
moieties, etc. dehydrogenation of alcohols into aldehydes and ketones is of
SBA-15-supported Cu nanocatalysts have been employed for great value for synthetic chemists because traditional methods
the conversion of DMO to EG with Au as an additive.239 The employ oxidizing agents in stoichiometric quantities. Shen and
vapor-phase hydrogenation of DMO involves several reactions,
namely, hydrogenation of DMO to methyl glycol (MG)
followed by reduction of MG to EG and then ethanol.484−486
Side products are invariably formed in this process, including
1,2-butanediol (1,2-BDO) and 1,2-propanediol (1,2-
PDO).484,485,487 The 6Cu/SBA-15 catalyst (which has a Cu
loading of 6 wt %) achieved 75.4% conversion of DMO, with
39.2% selectivity for EG as the product. However, the 6Au/
SBA-15 catalyst exhibited considerably lower DMO conversion
(5.4%) but with 80% selectivity for MG under the optimized
conditions (Table 6).
An improved catalyst was obtained by inserting Au into 6Cu/ Figure 68. Schematic of SiNWAs/Cu as the catalyst in the reduction
SBA-15239 to yield a material designated CuAu/SBA-15. This of 4-nitrophenol to 4-aminophenol. Reprinted with permission from
ref 463. Copyright 2014 Royal Society of Chemistry.
was a far more active catalyst than either 6Cu/SBA-15 or 6Au/
SBA-15 under identical reaction conditions, as indicated by the
TOF values for the three systems. Cu−Au alloy NPs were
detected on the catalyst surface; the presence of Au is presumed
co-workers have reported that Cu NPs dispersed on rod-shaped
to help stabilize the relative abundance of Cu(0) and Cu+, and
La2O2CO3 catalyze the dehydrogenation of both primary and
to help control the surface transmigration of Cu species via
secondary alcohols with excellent selectivity and good isolated
hydrogenation.
yields, albeit at quite high catalyst loadings (14.5 mol %).492
4.4. Oxidation Reactions Mesitylene was used as the solvent due to the high
Oxidation is one of the most important processes in organic temperatures required (110−150 °C) for the reaction, while
chemistry and plays a central role in the design and styrene served as a hydrogen acceptor (Figure 72).
development of novel value-added products.488,489 Many La2O2CO3 nanorods were obtained by calcination of
traditional oxidants are based on Mn or Cr, which must La(OH)3 at 773 K for 4 h in air, which produced a square
typically be used in stoichiometric quantities and are often block composed of two (001) flat planes, two (110) side
accompanied by the generation of toxic and hazardous waste planes, and two (110) end planes (Figure 73). Cu NPs formed
products, rendering product separation arduous and making by the deposition−precipitation method presented a 4.5 nm
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hemispherical shape preferentially anchored on the La2O2CO3

nanorods.492
Resin-immobilized CuO NPs have been prepared by
exchanging Cu2+ ions onto SERALITE-SRC-120, a cation-
exchange resin in its H+ form.493 Further treatment with an
alkaline solution containing cyclodextrin produced a nano-
deposit of CuO NPs onto the resin. The high oxidation state of
Cu in this material was confirmed by XRD and XPS analysis.
Interestingly, related resin-immobilized Cu NPs were prepared
by replacing the alkaline treatment with a reducing step in the
presence of NaBH4 or hydrazine. This led to both CuO NPs
and Cu NPs with spherical shapes and diameters of 30 ± 5 nm,
bound to the porous resin with its multichannel structure
(Figure 74).
Figure 70. Reduction of C−C multiple bonds catalyzed by Cu NPs in
Oxidation of low molecular weight alcohols into aldehydes zeolite.
under neat conditions with 2.9 mol % catalyst proceeded well
with CuO NPs, while Cu NPs furnished aldehydes in poor Mesoporous nanomaterials have garnered major attention
yields (<10%). The reactivity of the reactants decreased rapidly due to their unique physical and chemical properties, including
as their aliphatic chain length increased (Figure 75). large pore volume, high surface area, and well-defined pore
Yao and co-workers have reported the dehydrogenation of networks.495−497 Das et al. have synthesized mesoporous Cu-
propargylic alcohols into ynones catalyzed by Cu NPs with tert- doped silicate materials with silica to Cu ratios of 20:1, 10:1,
butyl hydroperoxide (TBHP) as an oxidant.494 The reaction
proceeded under mild conditions at room temperature in
CH2Cl2. Cu NPs were prepared by reduction of Cu(OAc)2
with NaBH4 under basic aqueous conditions. TEM analysis
revealed the formation of spherical NPs of 20−30 nm, and a
mixture of Cu0 and Cu+ species was identified by XRD.
Secondary alcohols bearing aryl groups were oxidized with
short reaction times (1−3 h) and good yields, but the presence
of aliphatic substituents decreased the catalytic activity of the
Cu NPs (Figure 76). Primary propargylic alcohols were
oxidized to the corresponding aldehydes in much lower yields.
In an effort to develop a more sustainable approach, the authors
studied an alternative procedure using air as the oxidant and
toluene as the solvent. The yields were very good, although
longer reaction times were required (8 h vs 1−3 h). However,
recyclability experiments showed that the reaction yield Figure 71. Ethanol synthesis over Cu NPs inlaid into mesoporous
decreased significantly after the third run, even with prolonged Al2O3. Reprinted from ref 41. Copyright 2014 American Chemical
reaction times. Society.

and 5:1, abbreviated as CuMSC-1 (Cu mesoporous silicate

catalyst), CuMSC-2, and CuMSC-3, respectively.498,499 Due to
the well-organized 2D hexagonal framework and high surface
area of the silicate, the nanomaterials exhibit good catalytic
activity in cyclohexane oxidation (Figure 77). In a typical
oxidation of cyclohexane, H2O2 was used as a green oxidant and
acetonitrile as the solvent with Cu-integrated mesoporous
silicate catalysts having different nSi/nCu ratios, at various
temperatures. In all of the test cases (CuMSC-1, CuMSC-2,
and CuMSC-3), cyclohexanone was the major product
(selectivity usually above 70%) and cyclohexanol was formed
in smaller amounts.
Cyclohexanone oxidation was initially performed with 5 wt %
of the CuMSC-2 catalyst, which has an nSi/nCu molar ratio of 35
and produced the two products (cyclohexanone and cyclo-
hexanol) in a combined yield of only 29% with a total TON of
230 under the optimized reaction conditions. Increasing nSi/nCu
to 75 (CuMSC-1) reduced the combined product yield to 17%
but improved the TON to 276. Interestingly, the CuMSC-3
catalyst, which has the highest level of Cu integration (nSi/nCu is
5.5), achieved the lowest TON (<26).498 In addition, this well-
Figure 69. Transfer hydrogenation of carbonyl compounds catalyzed defined mesoporous solid catalyst exhibited a modest loss of
by Cu NPs in zeolite. activity after being reused five times.
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Table 6. Catalytic Performance of Reduced Catalysts for the Hydrogenation of DMOa

selectivity (%)
catalyst conversion (%) EG MG EtOH othersc TOFb (h−1)
6Cu/SBAA-15 75.4 39.2 60.8 0 0 23
6Cu0.9Au/SBAA-15 84.7 41.8 58.2 0 0 37
6Cu1.4 Au/SBAA-15 96.6 93.1 3.5 0.4 3.0 73
6Cu1.9 Au/SBAA-15 100 99.1 0 0.8 0.1 121
6Cu3.7 Au/SBAA-15 100 98.7 1.2 0 0.1 86
6Au/SBA-15 5.4 19.7 80.3 0 0 12
4.6Cu1.4Au/SBA-15 100 97.6 2.2 0 0.2 83
a
Reaction conditions: T = 453 K, WLHSVDMO (weight liquid hourly space velocity) = 0.6 h−1, P(H2) = 3.0 MPa, H2/DMO = 80. bThe turnover
frequency (TOF) was computed when the DMO conversion was below 30%. cOthers included the byproducts 1,2-PDO and 1,2-BDO.

The synthesis of mesoporous CuO nanomaterials and their

catalytic properties for the oxidation of cyclohexene with
oxygen under solvent-free conditions have been reported.500
The mesoporous CuO nanomaterials with different shapes
were synthesized using various amines in an aqueous solution at
room temperature. The rationale for the amine-induced
formation of CuO was shown by using different aliphatic
amines such as trimethylamine, triethylamine, diethylamine,
ethylamine, etc. (Figure 78). Amines play several roles to
facilitate the formation of CuO by providing an alkaline
reaction medium, controlling the formation of CuO from
Cu(OH)2, and finally assisting in the crystal growth of CuO.
For the synthesis of the materials, different copper salts,
namely, Cu(OAc)2, CuSO4, CuCl2, and Cu(NO3)2, were used.
Among them, CuCl2 gave CuO NPs that showed better
conversion and selectivity for the aerobic oxidation of
cyclohexane.500
Biomimetic synthesis has become an important theme, and a
variety of biological molecules such as peptides, proteins, amino
acids, DNA, and RNA have been used extensively for the
synthesis of diverse nanostructures due to their effects on the
nucleation and growth of nanostructures.501−504 Wang and Lin
have reported the synthesis of protein-containing pH-
responsive red fluorescent water-soluble Cu NPs using bovine
serum albumin (BSA) as the stabilizing agent for styrene
oxidation.68 In a typical synthesis of protein-immobilized Cu
NPs,68 the NPs are conjugated to BSA in aqueous solution and
N2H4·2H2O is used as the reducing agent for the preparation of
Cu NPs (Figure 79).
The fluorescence of BSA−Cu NPs was tunable according to
pH, and the intensity of their fluorescence improved rapidly
when the pH was reduced from 12 to 6. The oxidation of
styrene was investigated to study the catalytic activity of the as-
synthesized BSA−Cu NPs; conversions of 70% or more were
achieved, with around 70% selectivity for benzaldehyde as the
major product (Table 7).
The selective oxidation of styrene to benzaldehyde has been
performed using organic peracid as the oxidant.505 For example,
Ge et al. synthesized two types of copper-based metal oxide
nanoparticles (CuO and CuO/Co3O4 NPs) via a scalable
method, and explored their catalytic activity for the selective
oxidation of styrene and its derivatives to the aldehydes using
tert-butyl hydroperoxide (TBHP) under mild reaction con-
ditions (Figure 80).506 The typical preparation entailed mixing
an organic ligand ((Z)-4-amino-5-(hydroxyimino)-2-(4-(n-
octyloxy)phenyl)-2,5-dihydro-1H-imidazole 3-oxide (AHO-
DIO)) with a metal (copper and cobalt) acetate to form
metal−ligand complexes (M−LCs) which were then heated at
500 °C to furnish metal oxide nanoparticles; the particles
3760
Figure 72. Dehydrogenation of alcohols into aldehydes and ketones.
showed efficacy for selective oxidation of styrenes to
benzaldehyde and could be reused up to five cycles while
preserving their catalytic activity and selectivity.
Two-dimensional (2D) and three-dimensional (3D) nano-
composites have been widely employed in various catalytic
applications, environmental remediation, and supercapaci-
tors.9,507−512 However, the controlled synthesis of 3D
architectures via chemical methods remains a challenge for
material chemists because it is not straightforward to tune the
nucleation and growth of nanomaterials.512 Bal and co-workers
have reported a hydrothermal synthesis of 3D raspberry-like
CuCr2O 4 spinel NPs by using the cationic surfactant
cetyltrimethylammonium bromide (CTAB).513 The formation
of 3D raspberry-like CuCr2O4 spinel particles could be assisted
by CTAB, whose effects during the nucleation−growth of the
seed actually influenced the morphology of the final NPs
(Figure 81).
The synthesized (3D) raspberry-like CuCrO4 spinel NPs
were employed for the hydroxylation of benzene to phenol with
H2O2 in excellent yield and selectivity. These spinel NPs
exhibited negligible leaching into the solvent over 10 catalytic
reaction cycles, proving that they are true heterogeneous
catalysts.
Transition-metal-catalyzed hydroxylation of C−H bonds has
received considerable attention because of the industrial
importance of the ensuing alcohols or phenol products.514,515
In particular, the direct catalytic conversion of benzene to
phenol with molecular oxygen is a very significant development
as it produces a minimum amount of waste. Bal and co-workers
designed a unique protocol for immobilization of ultrasmall
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Figure 73. HRTEM images of the La2O2CO3 nanorod viewed along
the (a) [001], (b) [110], and (c) [010] orientations. (d) A rectangular
cross-section (10 × 15 nm) of the nanorod viewed near the [110]
orientation. (e) Illustration of the real shape of the La2O2CO3
nanorod. (f) Hemispherical Cu particles with a mean size of about
4.5 nm on the La2O2CO3 nanorod viewed along the [001] orientation.
Reprinted from ref 492. Copyright 2013 American Chemical Society.
Figure 74. Immobilization of CuO NPs and Cu NPs on porous resin.
Reprinted from ref 493. Copyright 2008 American Chemical Society.
Figure 75. Oxidation of alcohols to aldehydes.
CuO on CuCr2O4 spinel (SP) nanoparticles (with a size of ∼55
nm) for selective hydroxylation of benzene to phenol using air
as an oxidant.516 The loading of Cu (2.3%, 3.6%, and 7.6%) in
the nanoparticles was found to affect the catalytic performance
of the particles significantly.516 Copper(II) oxide nanoparticles
(with an average size of 2.5 nm) supported on a CuCr2O4
spinel nanoparticle catalyst showed the highest activity in the
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Review
Figure 76. Dehydrogenation of propargylic alcohols into ynones.
benzene hydroxylation reaction and was selected as a model
catalyst. The high activity of the catalyst was attributed to the
ultrasmall size of copper(II) oxide (2−4 nm) nanoparticles, and
their tuning with CuCr2O4 spinel nanoparticles played a central
role in activating air to generate the active oxygen moiety that
facilitated the formation of phenol (conversion 36% and
selectivity 78%) (Figure 82). The same group earlier reported
the oxidation of (i) ethylbenzene to acetophenone517 and (ii)
benzene to phenol518 in the presence of H2O2 as an oxidant in
acetonitrile solvent.
Similarly, Zhang et al. managed to deposit highly dispersed
CuO nanoparticles in the mesopores of SBA-15 (CuO/SBA-
15) by postgrafting under ultrasonication.519 The CuO NP
loading in SBA-15 ranged from 2.1 to 13.4 wt %. The as-
synthesized mesoporous CuO/SBA-15 catalyst was used to
Figure 77. Oxidation reactions catalyzed by a Cu-integrated
mesoporous silicate catalyst (CuMSC). Reprinted with permission
from ref 498. Copyright 2014 Royal Society of Chemistry.
promote the one-step liquid-phase hydroxylation of benzene to
phenol, achieving a high conversion of benzene (28%) and
good selectivity for phenol (95%). Moreover, it could be
recycled up to five times without any noteworthy loss of
conversion or selectivity.
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Catalytic dehydrogenation processes have become increas- development of MCRs has targeted prominent and novel
ingly important because of their industrial utility for converting structural frameworks, and these reactions have played a central
alkanes to their unsaturated counterparts.520 For example,
Damodara et al. have recently demonstrated the use of Cu NPs
for such reactions,212 in which they showed the synthesis of
stable and monodispersed Cu(0) nanoparticles on an alumina
support from copper aluminum hydrotalcite via a chemical
reduction process in ethylene glycol.212 The polyols were used
for the reduction of metal ions to metal nanoparticles in
addition to being a low-cost and easy-to-remove solvent and
stabilizing ligand.521 The as-prepared Cu(0)/Al2O3 catalysts
were used for the dehydrogenation of amines to imines/nitriles Figure 79. Facile protein-directed synthesis of stable and water-soluble
and alcohols to carbonyl compounds with a wide substrate red fluorescent Cu NPs. Reprinted with permission from ref 68.
scope, including long-chain alkylamines, benzylamines, hetero- Copyright 2014 Royal Society of Chemistry.
cyclic amines, and alcohols (Figure 83). The stability of Cu(0)/
Al2O3 was established by its reusability in the dehydrogenation
of amines and alcohols, thus rendering Cu(0)/Al2O3 as an role in the synthesis of heterocycles and natural products over
appealing substitute to expensive noble-metal catalytic proto- the past few decades.526−531 Most established MCRs are
cols for the acceptor- and oxidant-free dehydrogenation of catalyzed by reagents that produce waste which must be
alcohols and amines. disposed of when the reaction is complete, and which are not
Lu and co-workers synthesized Cu NPs on Cr2O3 from usually recyclable. These processes could potentially be made
copper−chromium−hydrotalcite and studied their catalytic more economical and greener by using heterogeneous Cu NPs.

Table 7. Styrene Oxidation Catalyzed by Various Supported

Cu NCs

product selectivity
(mol %)
styrene
Cu cluster conversion
Cu source loading (%) (mol %) a b c d
Cu(NO3)2 35 72 25 72 2 1
CuCl2 35 74 27 69 3 1
CuSO4 35 73 25.5 70 3 1.5
Cu(OAc)2 35 70 28 66 5 1
Figure 78. Proposed mechanism for amine-induced CuO or Cu(OH)2
formation and aerobic oxidation of cyclohexene catalyzed by CuO.
Reprinted with permission from ref 500. Copyright 2015 Royal Society Yus and co-workers have reported the synthesis of
of Chemistry. indolizines and heterocyclic chalcones, which are important
skeletons in natural products and biologically relevant agents,
via supported Cu-NP-catalyzed multicomponent reactions.532
activity for chemoselective deoxygenation of alcohols under
Cu NPs/charcoal catalyzed the synthesis of indolizines from
an inert atmosphere without any oxidant (Figure 84).215
pyridine-2-carbaldehyde or quinoline-2-carbaldehyde, secon-
Preliminary studies involving benzyl alcohols as substrates
dary amines, and alkynes in CH2Cl2 at 70 °C at a low catalyst
showed that the kinetics of the reaction was dependent on the
loading. Good yields were obtained with a large selection of
nature of the substituents (electronegative substituents are
partners as shown in Figure 85.
relatively difficult to oxidize). The substrate scope of the
The synthesis of heterocyclic chalcones from pyridine-2-
reactions is shown for benzyl alcohols and other primary and
carbaldehyde derivatives and terminal alkynes was accom-
secondary alcohols (including alkyl ones) with moderate to
plished with Cu NPs/C as the catalyst and piperidine as a base
excellent yields (Figure 84 b). The nanocatalysts could also be
under neat conditions (Figure 86). Unfortunately, the Cu NP/
recycled five times without losing their activity.
C catalyst was not recyclable under the developed conditions,
4.5. “One-Pot” Multicomponent Reactions presumably because of significant Cu leaching.
Multicomponent reactions (MCRs) are powerful tools in An environmentally benign one-pot multicomponent syn-
organic synthesis that enable the preparation of biologically thesis of isoindolinone derivatives using cubic cuprous oxide
active heterocyclic compounds with huge structural variety and NPs as catalysts in an aqueous medium has been reported.85
molecular complexity via one-step transformations.522−525 The catalysts were prepared using a simple hydrothermal
MCRs construct molecular architectures rapidly and con- procedure where Cu(OH)2 was obtained via basic hydrolysis of
vergently from readily accessible raw materials, and in some CuCl2, and a follow-up treatment with fructose (as the
cases no isolation or purification of the products is needed. The reductant and capping agent) produced the final cubic Cu2O
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Figure 80. Preparation of copper-based metal oxide nanoparticles and their catalytic activity for styrene oxidation. Reprinted with permission from
ref 506. Copyright 2015 Wiley-VCH Verlag GmbH & Co. KGaA.
NPs. The nanocatalysts were successfully employed in the
synthesis of isoindolinones using 2-iodo-N-arylbenzamides, a
terminal alkyne, and substituted indoles/pyrroles (Figure 87).
The reactions with pyrroles, 3-substituted indoles, and
unsubstituted or N-substituted indoles took place at the C-2,
C-2, and C-3 positions, respectively. The reasonable con-
versions in the case of aliphatic alkynes further demonstrate the
versatility of the reaction. Interestingly, no alkyne dimerization
(Glaser coupling) was observed during the reactions. The
catalysts were assessed for their reusability under both aerobic
Figure 81. Generation of the 3D raspberry-like CuCrO4 spinel
catalysts. Reprinted from ref 513. Copyright 2014 American Chemical
Society.
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Review
and inert conditions and found to provide a better yield under
inert conditions (82% after the fourth cycle) as compared to
aerobic conditions (72% after the fourth cycle). The ascribed
mechanism entailed domino Sonogashira, 5-exo-dig cyclization,
and finally the regioselective nucleophilic addition of indoles or
pyrroles.
Cu2O NPs have been used as efficient catalysts for the
regioselective synthesis of α-carbonylfurans from propionates
and propynols.533 The catalysts were prepared by a simple
hydrothermal method534 which involved the one-pot sequential
PBu3-catalyzed formation of 1,5-enynes, followed by the Cu2O-
catalyzed cyclization of the latter into α-carbonylfurans.
Diversely decorated furans were accessible through this efficient
and regioselective methodology irrespective of the electronic
nature of the two partners’ substituents (Figure 88).
Liu et al. reported a domino synthetic strategy to access furan
derivatives from ene−yne ketones using Cu(I)-based magneti-
cally separable nanocatalysts that were prepared in one step
using Fe(II), Fe(III) and Cu(I) salts as metal precursors and
(TMA)OH (tetramethylammonium hydroxide) as the capping
agent.535 In their initial optimization step, 3-oct-2-ynylidene-
pentane-2,4-dione was elected as the substrate to monitor not
only the activity but also the selectivity of the catalytic process
(Figure 89). THF and L-proline have been shown to be the best
solvent and additive, respectively, and the selectivity of the
reaction was altered simply by changing the reaction conditions
from an aerobic to an inert atmosphere. The substrate scope of
the reaction was extensively studied, which showed that the
Figure 82. Ultrasmall CuO supported on CuCr2O4 spinel (SP)
nanoparticles catalyzed selective hydroxylation of benzene to phenol
with air.
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catalytic domino reaction with functional groups at different
positions of the alkyne terminus and carbonyl carbon could
lead to the regioselective formation of furan derivatives. In their
proposed mechanism (Figure 90), after the initial coordination
of Cu(I) species with carbonyl oxygen and a triple bond (A), an
intramolecular 5-exo-dig cyclization process allows the
formation of either a 2-furylcarbene complex (B) or a
zwitterionic intermediate (C). In the presence of air, relatively
unstable B undergoes aerial oxidation to afford the final
product, whereas 1,2-H migrations from the adjacent carbon
allowed the intermediate C to form the other regioisomer.
The magnetic properties of copper ferrite NPs allow them to
be separated from the reaction mixture and recovered with the
simple use of an external magnet.536 NPs with diameters of 35−
50 nm were prepared by thermal decomposition of Cu(NO3)2
and Fe(NO3)3 in aqueous sodium hydroxide without any
surfactant or capping agent.536 Their elemental distribution was
determined by EDS analysis, which suggested a formula of
CuFe2O4. This nanocatalyst was then used to promote a three-
component reaction that forms spiropyrimidines from anilines,
formaldehyde, and cyclohexanones. EtOH proved to be the
solvent of choice for achieving good yields while facilitating
catalyst recovery. Both electron-rich and electron-poor anilines
reacted efficiently with cyclohexanone, 4-methylcyclohexanone,
or 1,4-dioxaspiro[4.5]decan-8-one and formaldehyde (Figure
91). ICP-AES analysis of residual metal species in the reaction
supernatant revealed it to have Fe and Cu contents of less than
Figure 83. Dehydrogenation of (a) primary and secondary amines, (b)
indolines, carbazole, and quinolones, and (c) primary, aromatic, and
secondary alcohols.
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Review
0.5 ppm, suggesting that the catalyst is reasonably robust. XRD
and SEM analyses of the catalyst before and after reaction
confirmed that the NPs conserved their shape and size in
keeping with their retention of activity after five recycles.
Due to their wide spectrum of biological activity, α-amino
phosphonates have been the subject of numerous synthetic
investigations. While the traditional route for their synthesis
Figure 84. Cu(0)/Cr2O3-catalyzed dehydrogenation of alcohols
without an external oxidant.
involves the Lewis acid-catalyzed addition of diethyl phosphate
to imines,537−545 Kidwai et al. have developed a mild Cu-NP-
catalyzed method.546 Cu NPs were prepared by reduction of an
aqueous CuSO4 solution with hydrazine in the presence of
Triton X-100 as a surfactant, and the size of the NPs was
controlled by adjusting the molar ratio of water to surfactant.
Spherical NPs of 10, 20, 30, and 40 nm sizes were obtained, and
the maximum reaction rate was associated with particles 20 nm
in diameter. The three-component reaction involving benzal-
dehydes, anilines, and diethyl phosphate in acetonitrile at 50 °C
furnished the corresponding α-amino phosphonates in excellent
yields (Figure 92). Interestingly, the use of Lewis acids such as
Mg(OTf)3, AlCl3, Yb(OTf)3, or even Cu turnings instead of Cu
NPs resulted in significantly diminished yields.
Copper ferrite NPs, prepared by coprecipitation of Cu-
(NO3)2 and Fe(NO3)2 in an aqueous sodium hydroxide
solution, were catalytically active in the three-component
synthesis of spirooxindoles despites their rather large size (35
nm).547 The three-component process involving the use of
cylohexane-1,3-diones with cyanomethanes and isatins was
conducted in refluxing water and enabled the synthesis of more
than 38 oxindoles in high yields and purity (Figure 93). After a
simple filtration, the nanocatalyst was easily recovered from the
reaction mixture with an external magnet, washed with CHCl3
and H2O, and reused for another batch; the reaction yield was
constant until the fourth cycle and decreased slightly from the
fifth reuse onward.
Nanosized Cu NPs were employed in a one-pot three-
component synthesis of thiazolidine-2,4-dione (TZD) deriva-
tives,548 popularly known as glitazones, which are used as
chemotherapeutics for the treatment of type 2 diabetes
mellitus.549,550 Cu NPs (14 ± 2 nm) were also used to
catalyze a one-pot three-component reaction between
thiazolidine-2,4-dione, amines, and aldehydes without forming
any toxic waste or side products (Figure 94). Substrates bearing
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Figure 85. Synthesis of indolizines catalyzed by Cu NPs/C.
both electron-donating and electron-withdrawing groups were
successfully converted into the corresponding products in good
to excellent yields (64−91%).
Figure 86. Synthesis of heterocyclic chalcones from pyridine-2-
carbaldehyde derivatives and terminal alkynes.
Benzofuran and its derivatives, including substituted oxygen
heterocyclic compounds, play an important role in various
pharmaceutically active molecules,551−553 as antioxidative,554,555
anticancer,556,557 and anti-inflammatory558,559 agents. Copper-
(I) oxide NPs (CuO NPs) have been employed in multi-
component coupling/cycloisomerization reactions leading to
the synthesis of 2,3-disubstituted 1-benzofurans,560 showing
that Cu promoted a vital step in this methodology, namely, C−
H activation and an O-annulation protocol. The corresponding
substituted 1-benzofurans were obtained in excellent yields with
high atom economy under solvent- and ligand-free conditions
Figure 87. Multicomponent synthesis of isoindolinone derivatives
using Cu2O NPs as nanocatalysts.
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at 100 °C in air, and the CuO NPs could be recycled effectively
for at least five reaction cycles (Figure 95).
A3 couplings are multicomponent reactions that afford
propargylamines, key building blocks for the synthesis of
diverse bioactive compounds, nitrogen-containing heterocycles,
and natural products. Propargylamines are traditionally
synthesized by condensing an amine and an aldehyde to form
an imine, which is then attacked with a metal acetylide prepared
by deprotonating a terminal alkyne with a strong base such as n-
butyllithium (Figure 96). Such processes use stoichiometric
quantities of organometallic reagents that are difficult to handle
due to their air and moisture sensitivity, and produce large
quantities of waste. The A3 coupling is an attractive alternative
metal-catalyzed procedure that achieves the same trans-
formation under much milder conditions. Numerous innovative
variations of the A3 coupling and tandem reactions
incorporating this process have been developed.561 Cu catalysts
have played a noteworthy role in the development of A3-type
coupling reactions.
Figure 88. Regioselective synthesis of α-carbonylfurans from
propionates and propynol, catalyzed by Cu2O NPs.
A Cu NP/MagSilica catalyst was recently reported to be an
effective promoter of the A3 coupling under thermal solvent-
free conditions.361 The three-component process proceeded in
reasonable yields at 100 °C in air (Figure 97), using both
aliphatic and aromatic terminal acetylenes with secondary cyclic
amines such as morpholine and pyrrolidine. Acyclic secondary
amines gave more modest yields. The catalyst could be
separated from the reaction medium using an external magnet.
For the three-component reaction of p-tolylacetylene, benzal-
dehyde, and morpholine, the reused catalyst exhibited a
progressive but slow deactivation, with the yield falling from
83% for the first run to 77% for the third.
In another example, Guo et al. prepared monodisperse Cu
NPs using trioctylphosphine (TOP) and bromide ion (Br−)
from copper bromide in a disproportionation reaction.562
Highly monodispersed Cu NPs with spherical morphology and
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Figure 89. Furan derivatives from ene−yne ketones, catalyzed by Cu2O@Fe3O4.
Figure 90. Proposed mechanism and origin of selectivity for the Cu2O@Fe3O4-catalyzed synthesis of furan derivatives from ene−yne ketones.
a narrow size distribution were obtained; the selected area
electron diffraction (SAED) pattern determined for these Cu
NPs (Figure 98) features a series of diffraction rings
corresponding to a face-centered cubic (fcc) Cu structure,
indicating a high level of purity. These NPs were then
supported on silanized silica aerogel to yield a SiO2@Cu
nanocatalyst, which was tested in the A3 coupling reaction.
During optimization of the SiO2@Cu-catalyzed A3 coupling,
it was observed that although reasonable yields of the final
products were obtained under solvent-free conditions, excellent
yields were obtained in toluene. This was attributed to the high
dispersibility of SiO2@Cu NPs in toluene, which increases the
nanoparticles’ effective surface area. Using these materials as
catalysts, various aldehydes reacted with morpholine or
piperidine and phenylacetylene, affording the desired products
in good yields (Figure 99).563,564
Similarly, magnetite-supported Cu NPs were found to be
effective catalysts of a multicomponent acetylene−Mannich
reaction between secondary amines, terminal alkynes, and
aldehydes.565
Li and Organ have designed strongly MW-conducting thin
metal films of Cu and gold that can withstand temperatures
above 900 °C and have been successfully employed in the
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three-component coupling of terminal alkynes, amines, and
aldehydes.566 This protocol can be performed by using three
separate reactants, or by simply mixing the reaction
components before the reaction and infusing the reaction
through one single syringe. This procedure should be readily
scaled up for larger applications.566
Cu/MCM-41 NPs have also been used in the synthesis of
propargylamines via an A3 coupling multicomponent reaction
with amines and aldehydes under solvent-free conditions.567
The preparation of nanosized Cu/MCM-41 with various Si/Cu
molar ratios was achieved by direct insertion of Cu ions via a
sol−gel protocol with tetraethylorthosilicate (TEOS) as the
silica source and cetyltrimethylammonium bromide (CTAB) as
the template.567 Nanosized Cu/MCM-41 materials with Si/Cu
molar ratios of 10, 20, and 30 were designated 10-CM, 20-CM,
and 30-CM, respectively, and used for A3 coupling under
optimized reaction conditions without any added base or
solvent (Figure 100). The acidity and the total number of acid
sites of 10-CM, 20-CM, and 30-CM were determined by
potentiometric titration;568 20-CM proved to be more acidic
than the other samples.
The catalytic activity of the CuO−Fe3O4 composite
supported on GO was investigated for the A3 coupling reaction
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Figure 91. Synthesis of medicinally important spiropyrimidine
scaffolds by CuFe2O4.
Figure 92. Synthesis of α-amino phosphonates catalyzed by Cu NPs.
to synthesize propargylamines.569 Initially, graphene oxide
(GO) materials, synthesized using Hummer’s methods, were
coated with Fe3O4 NPs via a hydrothermal route. The Fe3O4/
GO material was then treated with CuCl2·2H2O, followed by
reduction using NaBH4, and subsequent thermal treatment of
the reaction mixture at 100 °C afforded Fe3O4 NPs/GO−CuO
nanocatalysts. The activity of the nanocatalysts was explored for
the reactions among different amines, various aldehydes, and
phenylacetylene (Figure 101). While aryl aldehydes worked
better as compared to aliphatic counterparts, halogenated
aldehydes were also tolerated by the reaction. The magnetic
separation offered easy recovery of the catalysts, and the
catalysts could be recycled at least four times without any
significant loss of activity.
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Figure 93. Copper ferrite NP-catalyzed three-component synthesis of
spirooxindoles.
4.6. Miscellaneous Reactions
This section describes other reactions catalyzed by Cu and Cu-
based NPs, including ring-opening reactions, domino or
sequential cyclizations, condensations, the hydrolysis of
ammonia−borane, protodecarboxylation of 2-nitrobenzoic
acid, and amination of aryl halides.
Mitra and co-workers have reported the reductive cleavage of
isoxazoline and carbonyl azide and domino cyclization to obtain
the corresponding 2-hydroxy-4-keto esters, primary amides, and
a heterocycle, 4-hydroxy-2-pyrroline-5-one, catalyzed by Cu
Figure 94. Synthesis of thiazolidine-2,4-dione derivatives.
NPs fabricated in situ in aqueous media.570 The progress of a
typical reaction is shown schematically in Figure 102; Cu NPs,
CuSO4·5H2O, SDS, and ascorbic acid (I) serve as raw materials
for the preparation of Cu NPs inside the supportive
assembly222 by reduction of the CuSO4 followed by nucleation,
growth, and quenching at 60 °C (II). The excess of surfactant is
then removed from the top portion of the NPs (III). The
solubility problem of the hydrophobic-phase organic precursor
in the aqueous medium was resolved by constructing a
surfactant-bound lipophilic environment (III).571
Metal-catalyzed ring-opening and domino or sequential
cyclization approaches are crucial tools in the synthesis of
hetero- and carbocyclic frameworks.572 Cu NPs can facilitate
several types of such reactions, including heteroatomic cleavage
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Figure 95. Synthesis of benzofuran and its derivatives using CuO NPs
as a catalyst. Figure 97. Cu NP/MagSilica-catalyzed synthesis of propargylamines
from aldehydes, alkynes, and amines.
of N−O bonds and homoatomic N−N bonds and domino
cyclizations to afford the desired products in good to excellent
yields.
Gawande and co-workers have reported a facile and
sustainable protocol for the synthesis of pyrazole derivatives
using magnetically separable and reusable magnetite-supported
Cu (nanocat−Fe−CuO) NPs under benign reaction con-
ditions.213 High-angle annular dark-field scanning transmission

Figure 96. Synthesis of propargylamines.

electron microscopy (HAADF-STEM) images of nanocat−Fe−

CuO clearly show the uniform distribution of Cu on the surface
of magnetite (Figure 103). Nanocat−Fe−CuO NPs with an
average size of 20−30 nm were prepared using simple
impregnation techniques490 in aqueous media from inexpensive
precursors and employed for the synthesis of pyrazole
derivatives (Figure 83).213
The reaction’s substrate scope using nanocat−Fe−CuO
magnetic NPs was explored, and it was shown to accommodate
structurally and electronically diverse aldehydes as well as
malononitrile and dimedone under solvent-free conditions
(Figure 104). The magnetic nanocat−Fe−CuO recyclable
catalyst was found to be stable and retained its initial catalytic
activity even after several runs.
Dumesic and co-workers have reported Cu NPs supported
on silica spheres (Cu/spSiO2) by atomic layer deposition
(ALD), which prevented sintering and leaching.573 The Cu/
spSiO2 catalysts were synthesized by ion exchange, encompass-
ing Coulombic metal−support interactions. The addition of
bifunctionality is an important and promising step toward
increasing the scope of heterogeneous catalysis because it opens
the door to more fine-grained control over the catalysts’
selectivities. Figure 105 shows the high dispersion of the Cu
NPs after reduction in Cu/spSiO2. After reduction, the catalyst
was coated with amorphous aluminum by alternately immersing
it in trimethylaluminum (TMA) and water 30 times, giving it a
restrictive and compressive aluminum oxide overcoat (30AL-
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Figure 98. Monodisperse Cu NPs: (a) TEM image; (b) SAED
pattern; (c) vis−NIR (near-infrared) extinction spectra of the Cu NPs
dissolved in toluene; (d) TEM image of a two-dimensional superlattice
assembled on a carbon grid. The inset in (c) shows a photograph of a
toluene solution of the Cu NPs. Reprinted with permission from ref
562. Copyright 2013 Royal Society of Chemistry.
DAlOx/Cu/spSiO2). Finally, heat treatment in air at 973 K
rendered the overcoat porous, providing access to the
encapsulated Cu particles (30ALDAlOx/Cu/spSiO2-973).
The addition of NbOx into the pores of 30ALDAlOx/Cu/
spSiO2-973 and calcination at 1173 K afforded 5ALDN-
bOx(30ALDAlOx/Cu/spSiO2-973)-1173, which has acidic sites
suitable for the etherification of furfuryl alcohol with 1-butanol
to provide the corresponding furfuryl butyl ether. The
etherification rate was found to be approximately an order of
magnitude higher than that achieved with 30ALDAlOx/Cu/
spSiO2-1173 after the addition of five cycles of NbOx.
Kaya et al. have reported a Cu−SiO2/CoFe2O4 nano-
composite material, Cu NPs@SCF, for the hydrolysis of
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Figure 99. SiO2@Cu-catalyzed A3 coupling reactions.
ammonia−borane (AB) (NH3·BH3) (Figure 106).574 The
material was synthesized by wet impregnation protocols via
in situ reduction of Cu(II) with AB on the surface of the SiO2/
CoFe2O4 nanocomposite. Cu NPs@SCF was found to be a
highly efficient catalyst for the hydrolysis of AB (Figure 85)
with an extraordinary initial turnover frequency (TOF = 2400
h−1), which was the highest value reported for this reaction with
such a low catalyst concentration (0.31% mol) and temper-
ature. Additionally, the release of hydrogen was accomplished
in consecutive cycles, with the Cu NPs@SCF catalyst being
recovered with an external magnet between runs. The catalyst
displayed exceptional stability with regard to leaching and
sintering, retaining 98% of its initial activity even after being
used 10 times.
Prechtl and co-workers have reported that copper(I) oxide
NPs (Cu2O NPs) embedded in ionic liquids (ILs) are effective
for the protodecarboxylation of 2-nitrobenzoic acid.575 The
nanoscale Cu catalyst was prepared by thermal decomposition
of basic copper carbonate in various ionic liquids without any
additional reducing agent. Among six ILs, only alkylphospho-
nium-based ILs, namely, n-Bu4POAc and (n-Bu4P)2SO4, could
decompose CuCO3 into Cu2O NPs at 120 and 160 °C,
respectively. Finely divided Cu2O NPs (with an average
diameter of 5.5 nm in n-Bu4POAc and 8 nm in (n-
Bu4P)2SO4) were evaluated for the protodecarboxylation of
2-nitrobenzoic acid and showed comparable activity. Quantita-
tive conversion was achieved with 3 equiv of Cu2O NPs in n-
Bu4POAc, and the catalyst could be recycled in nine
consecutive runs with a similar efficiency. Substrate screening
with 1 equiv of Cu2O NPs in n-Bu4POAc revealed that 2-
nitrobenzoic acids were prone to protodecarboxylation in low
to modest conversion (10−65%), while other benzoic acids
were essentially unreactive (Figure 107).
The same catalytic system was used for the amination of aryl
halides with aliphatic amines under ligand-free and relatively
mild conditions (Figure 108).121 With catalyst loadings as low
as 5 mol %, the amination of iodobenzene with a variety of
primary aliphatic amines proceeded with good to excellent
conversions (65−99%). Secondary aliphatic amines did not
readily afford acceptable conversions of the desired aniline, but
cyclic amines such as piperidine provided the targeted aminated
product with satisfactory yields. Aryl bromides and aryl
chlorides were sluggish in the reaction, but electron-rich aryl
iodides were excellent substrates. Unfortunately, the amination
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Figure 100. Propargylamine synthesis catalyzed by Cu/MCM-41
nanoparticles.
Figure 101. A3 coupling catalyzed by Fe3O4 NP/GO−CuO
nanocatalysts.
of aryl iodides bearing electron-withdrawing groups was not
reported in this study.
Sarkar et al. reported recyclable copper(I) oxide-catalyzed
synthesis of amides via amidation of aryl halides with
isocyanides in water (Figure 109)576 in the absence of
additional stabilizing ligands or additives and organic solvents;
amides were obtained in good yields (74−88%) for a variety of
aryl or aliphatic isocyanides and aryl halides. The catalysts
displayed recyclability up to four reaction cycles; however, the
minimal loss of activity has been ascribed to surface passivation
under the reaction conditions.
Quinazolines and their derivatives comprise important
biologically active compounds that form the cores of drugs
such as icotinib, lapatinib, and prazosin.577−579 Quinazolines
possess anti-inflammatory,580 antibacterial,579,581 antitumor,582
antiplasmodial,583 and antimicrobial and antioxidant584 proper-
ties. Supported CuO NPs were catalytically deployed for the
synthesis of quinozolines from 2-aminobenzophenones and
benzylic amines under oxidative conditions.585 CuO NPs on
kaolin were found to be better catalysts than CuO NPs/Al2O3,
CuO NPs/charcoal, and unsupported CuO NPs. Under
optimized conditions, the neat reactants were mixed using
tert-butyl hydroperoxide (TBHP) as the oxidant (Figure 110).
A variety of diversely decorated partners with electron-donating
and electron-withdrawing groups provided quinazolines in
excellent yields. The rapid decrease of the catalyst’s activity
upon reuse was ascribed to the significant Cu leaching observed
by ICP-AES.
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Figure 102. Fabrication of Cu NPs and their catalytic activity.
Reprinted with permission from ref 570. Copyright 2012 Royal Society
of Chemistry.
Quinazolines, a unique structural motif among the nitrogen-
bearing heterocycles, are the building blocks of various natural
products and biologically active pharmaceuticals.586−588 The
development of non-noble-metal-based heterogeneous catalysts
for the synthesis of quinazolines offers significant advantages.
For example, Zhang et al. reported the synthesis of quinazolines
using CuO nanocatalysts via coupling of aromatic alcohols/
aldehydes and amidines;589 The process was initially developed
Figure 103. HAADF-STEM images of nanocat−Fe−CuO, showing
the elemental mapping of Cu, Fe, and O. Reprinted from ref 213.
Copyright 2013 American Chemical Society.
for the coupling of aromatic aldehydes and amidines. The
presence of electron-donating groups on the para position of
aromatic aldehydes showed slightly better efficiencies than that
of electron-withdrawing counterparts. The reaction showed
high functional group tolerance, good recyclability, and only
marginal leaching (∼2.7 ppm). The strategy was subsequently
extended to aromatic alcohols where the reaction proceeded via
aerobic oxidation of aromatic alcohol followed by coupling
(Figure 111).
In another example, Modi et al. prepared CuO nanoparticles
to catalyze the reaction between 2-halobenzamides and
(aryl)methanamines in an aerial environment for the synthesis
of 2,3-disubstituted quinazolinones.590 This synthesis of the N-
heterocycle includes a consecutive Ullmann coupling (between
2-halobenzamide and (aryl)methanamine), oxidation of the in
situ produced secondary amine to imine, and finally an
intramolecular nucleophilic attack of the amidic N−H on the
imine carbon, leading to 2,3-disubstituted quinazolinones
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Figure 104. Synthesis of pyrazole derivatives using magnetically
reusable magnetite-supported Cu (nanocat−Fe−CuO) NPs.
(Figure 112). The recyclability of the catalyst and tolerance
of a wide range of functional groups make this method efficient
Figure 105. STEM images: (a) Cu/spSiO2 reduced, (b) 30ALDAlOx/
Cu/spSiO2 (the inset shows an EDS map of the border), (c)
30ALDAlOx/Cu/spSiO2, surface Cu particle overcoated by aluminum
oxide. (d) EELS mapping of an overcoated Cu particle. Corre-
spondence of colors and elements: green, Al; blue, Si; red, Cu.
Reprinted from ref 573. Copyright 2014 American Chemical Society.
and cost-effective. Additionally, the reaction mechanism was
proven by various control experiments, such as the reaction
between 2-bromo-N-(p-tolyl)benzamide and benzylamine in a
N2 atmosphere, which afforded an Ullmann coupled product
that could also be cyclized under the same reaction conditions
(Figure 112).
1,3-Azoles and their derivatives are found in biologically
active compounds, natural products, and organic functional
materials, including fluorescent dyes and liquid crystals.591,592
They are often prepared by transition-metal-catalyzed coupling
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reactions; viable catalysts include salts and complexes of

nickel,593 ruthenium,594,595 rhodium,596−598 and palladi-
um.599−601 Copper oxide NPs were employed for the direct
C−H arylation and alkenylation of aromatic heterocycles using
aryl and alkenyl bromides602 to provide a variety of 1,3-azoles,
including benzothiazole, benzoxazole, 1-methylbenzimidazole,
and 1-methylimidazole, in moderate to excellent yields (Figure
113). The catalyst was recovered and reused without significant

Figure 106. Cu NPs@SCF catalyst for the hydrolysis of ammonia−

borane. Adapted from ref 574. Copyright 2012 American Chemical Figure 107. Cu2O-NP-mediated protodecarboxylation of 2-nitro-
Society. benzoic acid.

loss of catalytic activity. For the arylation of benzoxazole, better

yields were obtained with electron-withdrawing groups on aryl
bromides than with electron-donating groups. Excellent yields
were obtained with heteroaryl bromides, but aryl chlorides
failed to react.
Khatun et al.603 demonstrated the synthesis of benzoxazoles
and o-hydroxyanilides from o-haloanilides in water using CuO
NPs. The use of an inorganic base, namely, Cs2CO3, enabled
the selective formation of o-hydroxyanilides, whereas the
organic base TMEDA (N,N,N′,N′-tetramethylethane-1,2-dia-
mine) generated benzoxazoles as the major product (Figure
114). The versatility of the catalysts was well-supported by the
substrate scope of the catalysts under both the reaction
conditions. However, despite being active for five cycles, the
catalysts showed progressive agglomeration in successive cycles.
Wang and co-workers reported that oxygen-stable CuFe2O4
nanocomposites can serve as efficient catalysts for the synthesis
of benzoxazole, benzimidazole, and benzothiazole derivatives
accessible from ortho-substituted aminobenzenes and various
aldehydes (Figure 115).604 The catalysts displayed a fair
functional group tolerance, yielding the final product in
moderate to high yields. However, aliphatic aldehydes did not
give better conversion as compared to aromatic aldehydes. The
magnetic property of the nanomaterials assisted with the ease of
separation of the catalysts, which could be recyclable for the
10th cycle without compromising their activity.
Cubic Cu2O NPs were synthesized without surfactants, and
their catalytic applications were explored using the reaction of
methylene blue (MB) and hydrazine in aqueous media as a
testing platform.605 The blue color of MB faded after the
addition of hydrazine and eventually became colorless,
indicating the formation of leucomethylene blue (LMB) and
the progress of the redox reaction (Figure 116). The transition
from blue to colorless occurs due to the formation of LMB
upon periodic shaking, making this an example of a “clock”
reaction. Other forms of Cu, including bulk Cu2O, CuO, and
Cu(0), did not work in the clock reaction, demonstrating the
importance of the nanostructure of the cubic Cu2O NPs.
The mechanism of the “clock reaction” involves a redox
process without photoactivation,606 and cubic Cu2O plays an
important catalytic role in mediating the transfer of electrons
from hydrazine to MB to form colorless LMB. The catalyst
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Figure 108. Cu2O-catalyzed amination of aryl halides with aliphatic
amines.
remains active for many days in solution. Electron transfer
occurs because both the oxidant (MB) and the reductant
(hydrazine) have good affinities for the nanocubes’ surfaces
(Figure 116).
The cluster band gap of Cu(0) clusters and the Fermi levels
of different Cu species play commanding roles in various
catalytic processes that control the energies of their highest
occupied molecular orbital (HOMO) and lowest unoccupied
molecular orbital (LUMO), which are very different from those
of Au and Ag. López-Quintela and co-workers have reported
the reduction of MB to LMB by hydrazine, a reaction catalyzed
by Cu clusters with various numbers of atoms.607 Three
different types of Cu(0) clusters (CuCLs), namely, Cu5, Cu13,
and Cu20, were prepared by a reported electrochemical
procedure608 with some modifications. The role of the cluster
size was investigated under optimized conditions, with the key
observation being that Cu5 clusters were more efficient than
Cu13 clusters and no reaction occurred at all with the largest
clusters (Cu20).
This perceived size dependence of CuCL catalysis can be
explained by considering the mechanism of a cluster-mediated
electron transfer from the donor (N2H4) to the acceptor (MB),
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Figure 109. Copper(I) oxide-catalyzed synthesis of amides in an
aqueous medium.
which has to progress via the conduction band of the CuCLs
(Figure 117). Catalyst stability was investigated in a reusability
Figure 110. Synthesis of quinozolines from 2-aminobenzophenones
and benzylic amines under oxidative conditions.
study, and it was noted that the clusters retained their catalytic
activity for at least 42 cycles.
In the field of heterogeneous nanocatalysis, the recyclability
and recovery of the catalysts after each cycle and the
regeneration of the catalytic species (either by washing or by
pretreatment before the next cycle) need substantial consid-
erations. The recovery of the catalysts depends mainly on the
scale of the reaction, the reaction conditions, and whether the
catalysts are lost during washing/separation. In this context,
magnetically separable catalysts are useful because they allow
negligible loss of the catalysts. The washing step is also crucial
as it helps to remove the adsorbed species on the surface,
thereby exposing the catalytically active species for the next
cycle. The knowledge of the reaction mechanism, including the
contributions from different reactants, helps to decide whether
an additional pretreatment step is required. For example, for
reduction and oxidation reactions, the propensity of either the
reactant or the oxidant to react with the catalysts is a major
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concern for such reactions. For supported catalysts, information
about the interaction of Cu species with the support also allows
the researcher to eliminate the leaching of the species from the
support. All these parameters can dictate how recyclable the
Figure 111. Synthesis of quinazolinones catalyzed by CuO NPs.
catalysts can be. Presently, for catalysts to be called “recyclable”,
they should be able to maintain their activity for at least three
cycles. In addition, the physical and chemical properties of the
catalysts after the last cycle would have to be compared with
those of the initial catalysts to confirm that there no significant
changes have occurred during the reactions/cycles. This general
rule applies to Cu-based catalysts as well. Additionally, for
Cu(0)- and Cu(I)-based nanocatalysts, given the tendency of
Cu species to be oxidized, special attention is required to
maintain the Cu(0) or Cu(I) state. For a Cu(II)-based catalyst,
Figure 112. Synthesis of 2,3-disubstituted quinazolinones catalyzed by
CuO NPs.
a similar consideration becomes important, especially when the
reaction involves a strong reducing environment.
5. PHOTOCATALYSIS
The following sections highlight the roles of Cu-based
nanomaterials with special emphasis on photocatalysis. In
1972, Fujishima and Honda discovered the light-induced
catalytic water splitting phenomenon on a TiO2 electrode.609
This pioneering finding represented a milestone in the history
of semiconductor photocatalysis. Since then, great effort has
been devoted to the study of photocatalysis,610−612 causing the
field to develop rapidly and producing important insights into
photocatalytic mechanisms that have greatly expanded the
scope and applications of photocatalysis in various areas.613−616
Due to their unique physical and chemical properties, Cu and
Cu-based nanomaterials, in particular, retain an important place
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in many promising photocatalytic applications, e.g., hydrogen
generation from water, CO2 reduction, photocatalytic self-
cleaning, and plasmon-induced organic transformations.
Figure 113. C−H functionalization of 1,3-azoles with bromoarenes
and bromoalkenes.
Although they were briefly mentioned earlier, this section
summarizes recent developments in photocatalytic systems
based on Cu and Cu-based nanomaterials, their catalytic
properties, and the associated mechanisms.
5.1. Cu and Copper(II) Oxide/Hydroxide NPs as Cocatalysts
for the Hydrogen Evolution Reaction (HER)
Semiconductor photocatalysis is a very promising method for
sustainable H2 production via the hydrogen evolution reaction
(HER), from water or biofuels using solar energy as the only
energy input.615,616 However, the H2 production efficiency of
pristine (or unmodified) semiconductor photocatalysts is
usually limited, mainly because of the rapid recombination
rate of photogenerated carriers (i.e., electron−hole pairs). One
popular strategy for circumventing this problem involves
promoting the separation of photogenerated electron−hole
pairs in semiconductors by modifying them with noble-metal
(e.g., Pt) NPs.617 In view of the high cost and low abundance of
noble metals though, it would be highly desirable to find other
inexpensive materials that are based on earth-abundant and
inexpensive metals with similar functional capabilities.617,618
Recent studies have proven that Cu NPs are suitable
alternatives to noble metals for catalytic HER617 as illustrated
by the case of a Cu−TiO2 system (Figure 118). Because the
Fermi energy level of metallic Cu lies below the conduction
band of TiO2, the photogenerated electrons in TiO2 can be
easily transferred to the Cu NPs. The interfacial electron
transfer provides an increase in the separation of photo-
generated electron−hole pairs, thereby resulting in an enhanced
photocatalytic activity.
In 2004, Wu et al. showed that Cu NPs prepared by wet
impregnation followed by low-temperature H2 reduction could
improve the catalytic activity of TiO2.619 The HER catalytic
activity of Cu−TiO2 is about 10 times higher than that of
pristine TiO2 at the optimum loading amount of 1.2 wt % Cu.
Another publication reported the spontaneous oxidation of Cu
NPs by O2 under an atmosphere of air, providing credible
evidence for the formation of thin Cu2O shells surrounding the
Cu NPs.620 Recently, ion-exchange226 and electroless plating621
methods have been developed by two different groups to
prepare highly active Cu-NP-modified TiO2 photocatalysts for
HER; the resulting materials exhibited greater catalytic activity
than a Cu−TiO2 sample prepared via the wet impregnation
Figure 114. CuO-NP-catalyzed synthesis of benzoxazoles and o-hydroxyanilides from o-haloanilides.
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Figure 115. CuFe2O4-catalyzed syntheses of benzoxazoles, benzimi-
dazoles, and benzothiazoles in the presence of oxygen.
Figure 116. Left: Schematic representation of the “clock reaction”
(i.e., color fading and regeneration of MB). Right: Catalytic activity of
Cu2O nanocubes in the “clock reaction”. Reprinted from ref 605.
Copyright 2008 American Chemical Society.
method. This finding was attributed to the ability of the ion-
exchange and electroless plating methods to produce highly
catalytically active Cu NPs with smaller particle sizes and
greater dispersion over the TiO2 surface.
In addition to TiO2 NPs, TiO2 nanotubes,622 mesoporous
TiO2−ZrO2 mixed oxide,623 SrTiO3 NPs,624 mesoporous
Nb2O5,625 and ZnO NPs626 have been used as support
materials for Cu NPs to produce hybrid materials with
enhanced catalytic activity for HER. For instance, Gomathi-
sankar et al. investigated how placing various metal NPs
(including Cu NPs) on ZnO affected its HER-specific catalytic
activity in aqueous methanol solutions.626 The presence of Cu
NPs was found to significantly improve ZnO’s catalytic activity,
with the Cu-modified ZnO showing about 130 times better
activity than bare ZnO (Figure 119). A possible mechanistic
justification for this improvement assumes that the Cu NPs
serve as electron sinks for electrons generated by ZnO, and that
by doing so the Cu NPs on the ZnO surface inhibit the
recombination of photogenerated electron−hole pairs, increas-
ing the photocatalytic activity.
Besides surface modification of metal nanoparticles, another
effective strategy for enhancing the catalytic activity of a given
semiconductor photocatalyst is to couple the material with
other semiconductors to obtain composite materials with
properties better than those of the individual components. CuO
nanomaterials can be very useful in such contexts, improving
the catalytic activity of other metal oxides. As noted above,
TiO2 is one of the most widely studied semiconductor materials
for HER, and its activity can be significantly enhanced by
coupling with CuO NPs/clusters. This effect is partly
attributable to the formation of favorable reaction sites for
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Figure 117. Schematic energy diagram showing the catalytic activity of
different CuCLs (Cu5, Cu13, and Cu20) used for the MB reduction by
N2H4. Reprinted from ref 607. Copyright 2014 American Chemical
Society.
catalysis at the interfaces of the two semiconductor materials. In
the case of CuO−TiO2 composite semiconductor materials,
there is a contact electric field at the heterojunction interface,
which facilitates the splitting process. Since the conduction
band (CB) of CuO is situated below that of TiO 2 ,
photogenerated electrons in the CB of TiO2 can be driven by
the contact electric field to the CB of CuO, thus leading to
efficient separation of photogenerated electron−hole pairs and
enhancement of catalytic activity (Figure 120a).627
It should be pointed out that bulk CuO itself does not have
the ability to catalyze the splitting of water to generate
hydrogen because the CB edge of CuO is lower than the H+/
H2 potential. In sharp contrast, the CB edge of CuO clusters is
higher than that of bulk CuO and the H+/H2 potential due to
the quantum confinement effect (Figure 120b). This is why
subnanosized CuO clusters are generally more effective at
improving TiO2’s catalytic activity. On the other hand, once the
photogenerated electrons are transferred to CuO from TiO2,
the Fermi level of CuO will be raised and its CB potential will
become more negative due to the accumulation of excess
electrons.628 This negative movement of CuO’s CB potential is
also beneficial for the reaction of photogenerated electrons with
protons to produce H2. For example, Xu et al. synthesized
CuO-modified TiO 2 NPs (Degussa P25) by the wet
impregnation method and found that the resulting composite
material gave a substantial hydrogen evolution rate of 18.5
mmol/h/gcatalyst from a methanol/water solution.629 The same
group also showed that CuO-modified TiO2 nanotubes
exhibited enhanced HER catalytic activity, with a hydrogen
evolution rate of 64.2−71.6 mmol/h/gcatalyst.630 This was mainly
attributed to the unique 1D tubular structure and large BET
surface area of the TiO2 nanotubes relative to TiO2 NPs. Jin et
al. reported an eosin-sensitized CuO−TiO2 photocatalytic
system that is efficient for HER under visible light (>420
nm) irradiation with an apparent quantum yield of 5.1%.631
Like CuO NPs/nanoclusters, Cu(OH)2 nanoclusters have
been successfully shown to serve as cocatalysts and improve the
catalytic activity of TiO2 nanomaterials toward HER. The first
attempt to make such composite materials and study their
catalytic properties for HER was conducted by Yu et al. in
2011.632 These authors prepared Cu(OH)2-cluster-modified
TiO2 photocatalysts by a precipitation method using Degussa
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P25 TiO2 NPs as the host material. The resulting composite
material had a Cu(OH)2 loading of 0.29 mol % and showed an
HER catalytic activity in aqueous ethylene glycol solution that
was 205 times greater than that of pure TiO2, yielding a
hydrogen evolution rate of ∼3.4 mmol/h/gcatalyst with a
quantum efficiency (QE) of ∼13.9%. Inspired by this
pioneering work, other workers have used Cu(OH)2 nano-
clusters as cocatalysts to enhance the catalytic activities of TiO2
nanotubes633 and graphitic carbon nitride.634
5.2. Copper(I) Oxide NPs for HER
Cuprous oxide (Cu2O) is a typical visible-light-responsive p-
type oxide semiconductor with a band gap energy of 2.0−2.2
eV. In 1998, the Domen group reported for the first time that
Cu2O nanomaterials display visible light photocatalytic activity
for water splitting635 and catalyzed the splitting reaction
without any noticeable decrease in activity for 1900 h under
visible light irradiation (λ ≥ 460 nm). The system’s quantum
efficiency in the spectral range between 550 and 600 nm was
∼0.3%, and this pioneering work prompted additional reports
on newer methods for synthesizing nanostructured Cu2O
materials with enhanced catalytic activity. Zhao et al. reported
the facile synthesis of hierarchically branched Cu2O nanowires
(Figure 121), in which thin nanowires and nanosheets (NSs)
served as the backbone and the branches, respectively.636 These
Figure 118. Mechanism of HER photocatalysis by Cu NPs supported
on TiO2 NPs.
hierarchically nanostructured Cu2O species exhibited remark-
able catalytic activity for HER, far greater than that of
conventional Cu2O NPs and nanowires without branched
structures. In another related work, Zhang et al. reported the
photochemical synthesis of Cu2O microcubes derived from
CuWO4,637 which exhibited both high activity and excellent
stability for hydrogen production from a glucose solution under
visible light irradiation. The catalytic activity of the Cu2O
material was further improved by Zn doping (0.1 wt %),
leading to an apparent quantum yield of ∼39%. In addition, the
construction of Cu2O−noble-metal hybrid nanostructures has
proven to be a viable way of improving the catalytic activity of
Cu2O toward HER.638,639
Cu2O NPs have been used as inorganic sensitizers to extend
the light response range of wide-band-gap semiconductors such
as TiO2 and provide the latter with visible light catalytic activity.
The potential applications of such materials (e.g., Cu2O-
modified TiO2 NPs and nanotubes) as catalysts for hydrogen
evolution from water under sacrificial conditions have been
successfully demonstrated.640−642 The sensitization mechanism
of Cu2O643 involves the generation of electron−hole pairs on
Cu2O upon visible light irradiation. Because the conduction
band of Cu2O is more negative than that of TiO2, photoexcited
electrons in the conduction band of Cu2O will transfer to the
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conduction band of TiO2 through the Cu2O−TiO2 interface.
Once in the conduction band of TiO2, these electrons can
efficiently participate in the hydrogen evolution reaction.
5.3. Cu and CuOx NPs as Cocatalysts for the CO2 Reduction
Reaction
The reduction of carbon dioxide (CO2) to useful chemicals and
synthetic fuels could play an important role in reducing our
dependence on fossil fuels and the levels of CO2 in the
atmosphere.644 The rapid development of photocatalysis during
the past few decades has sparked increased interest in the
Figure 119. Effect of different metal nanoparticles on the HER activity
of a ZnO surface in an aqueous methanol solution. Conditions: ZnO,
20 mg; reaction time, 3 h; reaction temperature, 50 °C; methanol
concentration, 10 vol %. Reprinted with permission from ref 626.
Copyright 2013 Elsevier Ltd.
sunlight-driven conversion of CO2 into solar fuels. Since the
photochemical reduction of CO2 is an energetically uphill
process, there is a need for efficient photocatalysts to make it
possible. A number of recent studies have explored the
potential uses of Cu and CuOx NPs as efficient cocatalysts
for enhancing the activity and selectivity of semiconductor
catalysts for CO2 reduction. For example, Varghese et al.
reported the solar conversion of CO2 and water vapor to
methane and other hydrocarbons using nitrogen-doped titania
nanotube arrays as photocatalysts and platinum−Cu nanois-
lands as cocatalysts (Figure 122).645 This material achieved a
hydrocarbon production rate as high as 111 ppm/cm2/h from
CO2 under outdoor global AM 1.5 sunlight (100 mW/cm2). In
another example, Yang et al. prepared Cu−TiO2/SBA-15
composite photocatalysts that were used for photoreduction of
CO2 with H2O to methanol.646 The Cu NPs present in the
composite material served as cocatalysts, facilitating the
separation of electron−hole pairs and thereby enhancing the
composite materials’ catalytic activity. Besides methane and
methanol, Cu-NP-based catalysis can also produce other higher
alkane products and their derivatives. Zhang et al. reported
efficient photocatalytic CO2 conversion over a double-walled
TiO2 nanotube array modified with a bimetallic Cu−Pt
nanoalloy.647 The photocatalytic reaction occurs at room
temperature, producing CH4, C2H4, and C2H6 as the main
products. Under AM 1.5 one-sun illumination, a hydrocarbon
production rate of up to 0.16 mmol/h/gcatalyst was obtained
using Cu0.33−Pt0.67 as the optimal cocatalyst. Besides TiO2,
other metal oxide semiconductors such as ZnO and ZnO1-xNx
have also been modified with Cu NPs, and the resulting
materials were found to exhibit enhanced photocatalytic activity
in CO2 reduction.648
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Figure 120. (a) Charge transfer and separation in CuO−TiO2 under
UV light. (b) Energy levels of the conduction and valence band edges
vs the normal hydrogen electrode (NHE; at pH 0) for TiO2 and CuO
NPs of various sizes (the quantum size effect is reflected by the band
gap increase). Reprinted with permission from ref 627. Copyright
2011 Elsevier Ltd.
In another important study, Shown et al. recently
demonstrated that Cu-NP-modified graphene oxide (GO)
could serve as an efficient composite photocatalyst for the CO2
reduction reaction. 649 GO in this composite material
functioned as a wide-band-gap semiconductor, whereas Cu
NPs acted as cocatalysts. Cu NPs were believed to have
multiple roles, including suppressing the recombination of
photogenerated electron−hole pairs, reducing the GO’s band
gap, and modifying the GO’s work function. As a result, Cu
NPs could significantly enhance the photocatalytic activity of
GO. With an optimal Cu NP loading of 10 wt % (Cu/GO), the
solar fuel production rate achieved was the highest value (∼7
μmol/h/gcatalyst), which was >60 times higher than that of
pristine GO.
In addition to Cu NPs, Cu-based oxides (such as CuO and
Cu2O) have been found to be effective cocatalysts for
photocatalytic CO2 reduction. For instance, the synthesis of
hollow composite nanocubes of CuO−TiO2-xNx that can
photocatalytically convert CO2 into methane has been
demonstrated.650 Photocatalytic CO2 conversion under simu-
lated solar irradiation (AM 1.5G) at ambient temperature led to
methane production at a rate of 41.3 mmol/h/gcatalyst, which is
2.5 times faster than that obtained with Degussa P25 TiO2. It
should be noted that pristine CuO showed negligible activity.
However, no mechanistic details were included in this study. In
a separate study, amorphous copper(II) oxide nanoclusters
were found to function as efficient cocatalysts for the reduction
of carbon dioxide (CO2) to carbon monoxide (CO) when
grafted onto the surface of niobate nanosheets (Figure 123).40
The resulting composite material could afford a CO production
rate of about ∼0.7 μmol/h/gcatalyst. Some of the studies showed
that, under UV irradiation, the excited holes in the valence band
of niobate nanosheets reacted with water to produce oxygen,
and the excited electrons in the conduction band of niobate
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nanosheets were injected into the Cu(II) nanoclusters through
the interface, which subsequently reduced CO2 to produce CO.
A novel cocatalyst based on core/shell Pt/Cu2O has been
designed for photocatalytic CO 2 conversion that can
significantly promote the conversion of CO2 to CH4 and CO
has been reported recently.651 The Cu2O shell serves as a
reactive site for the activation and conversion of CO2 molecules
in the presence of H2O, and the Pt core functions as an electron
pool to receive the photogenerated electrons in the TiO2
photocatalyst. The core/shell cocatalyst markedly suppresses
the photoreduction of H2O to H2, which is a competitive
reaction with the reduction of CO2. Cu2O NPs themselves
could promote the photocatalytic activity of TiO2 toward CO2
reduction, as shown in two recent studies.652,653 In addition,
Figure 121. (a) Formation of hierarchical branched Cu2O NW
nanostructures. The digital camera picture on the right is of the
branched NWs produced in a single batch. (b) Typical high-
magnification SEM image and model (inset) of the as-grown Cu2O
NSs−NWs. (c) STEM image and (d, e) corresponding elemental
mapping for Cu and O in a single NS−NW. The scale bar represents
100 nm. Reprinted with permission from ref 636. Copyright 2014
Royal Society of Chemistry.
Uzunova et al. studied the mechanism of CO2 reduction to
methanol by H2O on copper(I) oxide nanolayers and clusters
using density functional theory.654 They found that the surface
of copper(I) oxide nanoclusters and nanolayers was stabilized
by the formation of Cu−Cu dimers and larger assemblies of
copper cations. The CO2 molecule underwent strong bending
upon adsorption on a Cu−Cu dimer site on the surface,
whereas the H2O molecule underwent dissociative adsorption.
The first step of CO2 hydrogenation was the formation of the
carboxyl group, −CO(OH), with a very small energy barrier
(13.8 kJ/mol). The further hydrogenation led to the formation
of formic acid, HCO(OH), with an activation energy of 121 kJ/
mol. The as-formed formic acid molecule remained adsorbed
strongly on the surface of copper(I) oxide nanoclusters and
nanolayers. The formic acid molecules on the Cu2O surface
could further be reduced by water, resulting in the formation of
formaldehyde and methanol.
5.4. CuOx-Based NPs for Self-Cleaning
Semiconductor-based photocatalysis has become a comple-
mentary technique to more conventional approaches (such as
high-temperature incineration) for the destruction of organic
pollutants.611 This is because photocatalytic, or self-cleaning,
methods allow the degradation of organic compounds adsorbed
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on the catalyst surface into CO2 and H2O using ubiquitous
solar energy at room temperature. In such self-cleaning systems,
O2 is usually the ultimate oxidant, reacting with photogenerated
electrons from the conduction band of the photocatalyst to
form reactive oxygen species such as O2•− and •OOH.
Simultaneously, the photogenerated holes in the valence band
of the photocatalyst react with surface water molecules,
producing another reactive oxygen species, •OH. As these
photoinduced reactive oxygen species are strong oxidants, they
can completely oxidize organics into CO2 and H2O, thus
achieving the self-cleaning purpose. Given that some important
oxide photocatalysts such as TiO2 and ZnO are unable to utilize
the main component of solar irradiation, visible light, Cu-based
oxides that respond to radiation in this band are very promising
photocatalysts for solar self-cleaning applications.
Several reports have shown that Cu2O nanostructures can
photocatalytically degrade organic pollutants such as methyl
orange and rhodamine B under visible light.655,656 The
photocatalytic activities of the Cu2O nanomaterials are
proposed to be dependent on their particle size, surface area,
porous structure, and crystal facets,197,655−658 and could be
further improved by coupling with metallic Cu or carbon
quantum dots.659,660 Chen et al. synthesized core/shell Cu/
Figure 122. Cocatalyst-loaded flow through a nanotube array
membrane for high-rate photocatalytic conversion of CO2 and water
vapor into hydrocarbon fuels. Reprinted from ref 645. Copyright 2010
American Chemical Society.
Cu2O nanowires that could serve as efficient visible light
photocatalysts for the degradation of methylene blue.659
Metallic Cu could facilitate the separation of photogenerated
electron−hole pairs, and thereby promote the activity of Cu2O.
In another example, carbon quantum dots/Cu2O could harness
near-infrared (NIR) light for photocatalytic degradation of
methylene blue (Figure 124).660 The catalytic activity was
mainly attributed to the up-converted photoluminescence of
carbon quantum dots. In addition, Cu2O NPs have been
coupled with wide-band-gap semiconductors such as TiO2 and
ZnO to form composite semiconductor materials with
enhanced photocatalytic activity for the elimination of several
organic compounds in water, including phenol, methyl orange,
and 4-nitrophenol.217,660−665 The function of Cu2O NPs in
these Cu2O-based composite nanomaterials for self-cleaning
applications is similar to that described in section 5.2.
5.5. Cu NPs as Plasmonic Photocatalysts for Organic
Transformations
The localized surface plasmon resonance (SPR) effect is a
collective oscillation of conduction band electrons in metallic
NPs,666−668 and it occurs when the frequency of incident
photons matches that of these oscillating conduction band
electrons in metallic NPs.669 The surface plasmon band of Cu
NPs is located in the range of visible light with a maximum of
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∼580 nm for spherical Cu NPs. Theoretically, the localized
SPR effect of Cu NPs could be employed to tune chemical
reactions that occur on the surface of Cu NPs. However, to
date there have only been two publications describing the
exploitation of this effect in selective organic transformations
mediated by Cu NPs.
Guo et al. synthesized graphene-supported Cu NPs by
reducing Cu2O/graphene composites in a mixture of H2 and Ar
at 500 °C192 and used them as plasmonic photocatalysts for the
selective synthesis of aromatic azo compounds from the
corresponding nitro compounds under visible light irradiation
(Table 8). The photocatalytic experiments were conducted in a
2-propanol solution under irradiation from a 300 W Xe lamp
(400−800 nm, 0.15 W/cm2) to promote the coupling of a
series of aromatic nitro compounds. This reaction was found to
be dependent on both the intensity and the wavelength of the
incident light, confirming that the coupling reaction was indeed
photodriven. Presumably, the localized SPR effect excited the
energetic electrons on the surface of the Cu NPs, which
facilitated the cleavage of the N−O bonds in the aromatic nitro
compounds, leading to the formation of azo compounds.
In another example, the selectivity of Cu/SiO2-catalyzed
propylene epoxidation (C3H6 + 1/2O2 → C3H6O) was
significantly improved by visible light irradiation,670 which
Figure 123. Amorphous copper(II) oxide nanocluster modified
niobate nanosheets for the reduction of carbon dioxide (CO2) to
carbon monoxide (CO). Reprinted from ref 40. Copyright 2015
American Chemical Society.
caused a sharp increase in the selectivity for propylene epoxide
from ∼20% to ∼50%. This was attributed to the localized SPR
produced on the Cu NPs, which weakens the surface Cu−O
bonds and promotes the reduction of surface Cu-based oxides
that are harmful to the epoxidation of propylene.
6. ELECTROCATALYSIS
Electrocatalytic reactions, which are accompanied by charge-
transfer processes, could potentially play important roles in
sustainable development and technological advancement.671
This is because a vast number of important chemical reactions
can be made possible by electrochemical processes, as
exemplified by the electrochemical reduction of CO2 into
synthetic liquid fuels, water splitting to generate molecular
hydrogen (and oxygen) from water, energy recovery in fuel
cells and solar cells, among others.672−676
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For decades, the catalysis of many such important processes
has relied on a handful of scarce and expensive noble metals
such as Pt or Ir; it was generally believed that their reactivity
could not be matched by base metals.677,678 However, a variety
of nanomaterials, specifically carbon-based materials, transition-
metal oxides, and chalcogenides, have recently been shown to
have outstanding catalytic activity for many of these reactions
with greater stability than the noble-metal alternatives.678−681
Cu-based nanomaterials are notable examples, as they have
already been proven to play important roles in many catalytic
processes relevant to sustainable technologies and energy
conversion processes.682 Generally, in electrocatalysis, the free
energy required to perform a chemical reaction is specified by
the standard electrode potential.683 However, as with conven-
tional reactions, additional energy is required to overcome
activation barriers and initiate the electrochemical reaction; this
is referred to as the overpotential.684 Thus, the potential that
must be applied above and beyond the standard thermody-
namic potential of the reaction is linked to the activation energy
of the process, while the reaction rate is related to the current
density on the electrode surface.685 A good electrocatalyst
would reduce the overpotential needed to carry out the reaction
and increase the current density. In addition, an electrocatalyst
could potentially facilitate a particular electron-transfer process
while hindering others.686 It can also entirely modify the
chemical products generated on an electrode surface at a
predetermined electrode potential, preferentially delivering the
desired products and increasing the selectivity of the process.
The development of nanomaterials for electrocatalysis is a
vibrant research field. However, much remains to be learned
about the origins of the catalytic activity of nanomaterials and
the nature of electron transfer in nanostructured do-
mains.687,688 This is partly because earlier studies were often
conducted on perfectly flat surfaces, so their results are not
applicable to nanomaterials, which have properties associated
with quantum size effects that prohibit straightforward
prediction.689,690
An area of particular relevance, where nanomaterial-based
electrocatalysis could find significant applications, is CO2
reduction. Many noble and non noble metals have been
investigated as catalysts for CO2 reduction over the years.691
Metals such as Pt, Ni, Fe, and Ti produce high cathodic current
densities when a reduction potential is applied to CO2-
saturated aqueous solutions, but this cathodic current is merely
due to the side hydrogen evolution reaction (HER) that occurs
in aqueous media.692 In addition, these metals also possess high
affinity for CO, leading to rapid losses of their catalytic activity.
Other metals such as Hg, In, and Cd have the advantage of
being less active toward hydrogen evolution reactions. Thus,
the competing effect of hydrogen production during the CO2
reduction process in aqueous media is a minor concern. Hence,
these materials, when applied as catalysts for the CO2 reduction
process, exhibit a strong tendency to generate formate and a
very low capability to generate hydrocarbons or C-2
molecules.692 In this respect, Cu has some very unique and
advantageous properties for CO2 reduction, including its ability
to promote the formation of hydrocarbons in CO2 electro-
reduction693 and its favorable potential for C−C bond
formation in CO2 reduction.694 Consequently, the reduction
of CO2 can be achieved on a Cu electrode, leading to the
formation of important organic compounds such as methane,
acetylene, and ethanol.695,696
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Figure 124. (a and b) SEM, (inset of (a)) TEM, and (c and d)
HRTEM images of a carbon quantum dot/Cu2O composite for self-
cleaning applications and (e) SEM image and (f−h) EDS element
mapping data for Cu, O, and C in a single composite particle.
Reprinted with permission from ref 660. Copyright 2012 Royal Society
of Chemistry.
Another important characteristic of Cu in electrocatalysis is
that its affinity for carbon monoxide (CO) is substantially lower
than that of other well-known metals such as Ru, Rh, Pd, and
Pt.697 This is beneficial for long-term stability of the
electrocatalyst since CO appears as a possible coproduct or
intermediate in many important electrocatalytic processes.698
For instance, in CO2 reduction, a certain amount of CO is
always produced as a reaction intermediate.699 The complete
electrochemical oxidation of organic compounds, a process
necessary in fuel cells using organic compounds as fuels, can
also produce CO as a reaction intermediate.700 As a result, the
adsorption of CO on the catalyst surface will increase the
overpotential needed to keep the reaction running and also
reduce the current density at a specific electrode potential,
besides possibly poisoning the catalyst.
The above discussion clearly shows that Cu is a promising
catalyst for CO2 reduction because it enables the production of
hydrocarbons at significant current densities, exhibits good
selectivity, and possesses a low surface affinity for CO.
Moreover, it is known to be a promising catalytic material for
fuel cells.701 However, the main challenges related to such
applications are to reduce the overpotential and control the
selectivity of Cu-based catalysts by increasing their energy-
transfer efficiency and improving the stability of specific
reaction intermediates. Considering this, the exploration of
Cu-based nanostructured systems may reveal a broad scope for
improving the performance of Cu-based electrocatalysts.
6.1. Electrocatalysis of Fuel-Cell-Related Reactions
Cu has long been recognized as a promising catalyst for the
electrooxidation of organic compounds.701 Electrodes modified
with Cu2O can provide stable and sensitive electrocatalytic
responses for the oxidation of carbohydrates, amino acids,
aliphatic diols, simple alcohols, amines, and alkyl polyethoxy
alcohol detergents.702 Xia et al. have proposed a mechanism for
the electrocatalytic oxidation of organic compounds by Cu in
alkaline media based on the formation of a CuO layer on the
Cu particles’ surfaces followed by the formation of adsorbed
•
OH radicals, which are responsible for the oxidation of organic
compounds.701 This incipient hydrous oxide/adatom mediator
(IHOAM) model attempts to explain the ability of Cu to
catalyze the oxidation at low overpotentials, and also predicts
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Table 8. Photocatalytic Coupling of Aromatic Nitro
Compounds over a Cu/Graphene Catalysta
a
The reactions were conducted under an argon atmosphere at 90 °C
using 30 mL of isopropyl alcohol mixed with 0.3 mmol of KOH, 3
mmol of nitrobenzene, and 100 mg of 5 wt % Cu/graphene catalyst.
The irradiation intensity was 0.15 W/cm2, and the reaction time was 5
h. Conv. = conversion, Select. = selectivity, and QY = quantum yield.
b
The other products are the corresponding aromatic azoxy
compounds.
that nanostructured Cu should show a stronger catalytic
effect.703 Burke et al. have discussed the electrocatalytic activity
of Cu in alkaline media at low overpotentials using the IHOAM
model,704,705 concluding that electrocatalysis mainly occurs at
defect sites. These defect sites, which are also considered to be
the active sites, serve as sources of energetic species, e.g.,
adatoms or clusters. In the case of nanostructured materials, the
IHOAM model affirms that as the particle size becomes
increasingly small, the catalytic activity increases due to the
reduction of the mean lattice coordination number, resulting in
a higher surface free energy. Consequently, the highly active
surface metal atoms and their oxidized phases, which are
referred to as incipient hydrous oxides, act as mediators in the
electrochemical reactions.
Electrooxidation of organic compounds has long been an
important topic considering that liquid fuel cells have to use an
electrocatalyst for the oxidation of the liquid fuels.706 Cu and
related nanostructured materials have proven their suitability as
electrocatalysts in direct methanol fuel cells (DMFCs) in
alkaline media.707 Nanostructures prepared by the electro-
chemical corrosion of a Cu electrode or by electrodeposition of
Cu NPs onto Cu electrodes can promote the enhancement of
the electrode activity due to an increase of the effective surface
area of the electrode.707 The crystal structure of Cu NPs
deposited via electrodeposition is an important factor in the
enhancement of the electrode activity toward methanol
oxidation. Venkatasubramanian et al. have compared the
electrocatalytic activity of plate-like Cu NPs and octahedron-
like Cu NPs,138 by measuring the cyclic voltammetric curves of
a bare gold electrode and electrodes covered with plate-like and
octahedron-like Cu NPs in a basic solution containing
methanol (Figure 125). The obvious differences among the
sample for current density and onset oxidation potential have
clearly indicated the catalytic effect of the Cu NPs vs the bare
gold electrode. The current density observed when plate-like
Cu NPs were used as electrocatalysts was about 2-fold higher
than the current density observed with octahedron-like Cu
NPs; the higher activity of plate-like NPs is ascribed to the
[111] and [110] crystal planes of Cu as compared to the [100]
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crystal plane of Cu for methanol oxidation. Hence, Cu NPs that
expose either the [111] or the [110] plane more than the [100]
plane should be better electrocatalysts for methanol oxidation.
The higher catalytic activity found for plate-like Cu NPs was
also justified by a greater exposure of the surface of the [111]
crystal plane than either of the [110] and [100] planes, while
octahedron-shaped Cu NPs with all three crystal facets were
almost equally exposed.
Thin nanostructured layers of Cu can easily be created on the
surfaces of different conduction materials for the preparation of
Cu electrodes. Cu electrodeposition at high cathodic potentials,
from an aqueous Cu salt solution, leads to a porous Cu
structure because of intense hydrogen evolution during the
deposition process. Niu et al. have demonstrated an intriguing
porous electrochemical interface based on Cu foams that can be
fabricated by electrodeposition processes at high cathode
potentials and applied to the sensing of glucose in alkaline
media.708 The hydrogen evolution process, which occurs
simultaneously with the Cu deposition, generates a highly
porous Cu interface, as shown in the SEM images (Figure 126).
The effects of the deposition conditions on the formation of
Cu NPs and the correlation of the particles’ geometry with the
activity toward methanol electrooxidation was evaluated by Xia
et al.,701 by using multilaminated Cu particles fabricated over
different conductive substrates. The electrodeposition was
conducted for the growth of Cu crystallites preferentially
oriented with the [111] planes parallel to the substrate surface.
A conducting polymer (poly(2-amino-5-mercapto-1,3,4-thiadia-
zole)) was used to increase the surface active area of the Cu and
reduce charge-transfer resistance during the methanol oxida-
tion. The presence of the polymer between the Cu NPs
resulted in a large increment in the current density of 196 mA
cm−2 at 0.838 V vs SCE (saturated calomel electrode), which is
one of the highest current densities ever reported for methanol
oxidation using a non-noble-metal catalyst.701
Periasamy et al.709 have presented a wet chemistry method
for preparing hierarchical Cu nanowires (Cu NWs) with rose-
like stem structures featuring nanothorns (Figure 127). In the
presence of catechin, which acts as a reducing agent, Cu
nanothorns grow from the [200] side faces of rose-like stems
that are partially capped by ethylenediamine (EDA). The
catechin and EDA concentrations, and the reaction time, can be
used to tune the size and morphology of the Cu NWs. Figure
128 shows TEM and SEM images of Cu NWs prepared under
different synthetic conditions. Cu nanostructures can also be
deposited over graphene oxide using a hydrothermal approach
where the graphene oxide itself is also reduced. The Cu NW/
reduced graphene oxide hybrid material provided a small
charge-transfer resistance when applied as an electrocatalyst for
methanol electrooxidation. The synthesized hybrid was
inexpensive and highly durable and had a low onset potential
(ca. 0.48 V vs Ag/AgCl) with a high mass activity (1.11 mA
mg−1), representing a potential electrocatalyst with superior
catalytic activity for methanol oxidation in alkaline media.709
In fuel cells as well as air batteries, the catalytic reduction of
oxygen can be a detrimental process, which can limit the
efficiency of these energy-converting and energy storage
systems.219,710−712 A Cu-NP-modified electrode was evaluated
as an electrocatalyst for the oxygen reduction reaction (ORR)
by Awad et al., using a Au(100)-rich polycrystalline gold
electrode modified by controlled electrodeposition of Cu
(Figure 129).713 First, a self-assembled monolayer (SAM) of
cysteine was deposited on the bare gold electrode. A partial
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desorption of the SAM monolayer was then performed to
expose part of the Au surface. Electroreduction of Cu was
conducted to deposit Cu in the areas where the cysteine was
not present. In the last step, the complete desorption of the
cysteine was carried out, leaving a modified Au electrode with
Cu nanoislands on it. The electrochemical evaluation of the Cu
NPs on gold was assessed for the electrochemical ORR, in
which the prepared electrode showed high catalytic activity,
similar to Pt electrodes. The high catalytic activity exhibited by
the prepared electrode was attributed to the relative enrichment
of (100) Au crystalline planes on the Cu NP/Au electrode due
the partial desorption of cysteine, which occurs more easily in
the other crystalline planes than (100), and thus, the remainder
of the cysteine molecules protected the (100) Au crystalline
plane from Cu deposition. Consequently, after Cu deposition
and complete removal of cysteine, the exposed surface of Au is
mainly composed of (100) crystal planes.713
Silver−copper alloys have been reported as highly active
particles for the oxygen reduction reaction, which can be
compared to platinum-based catalysts.711,714,715 Wu et al.
showed the use of AgCu nanoalloys as the active materials in
the air cathode of the zinc−air battery.716 The nanoalloys were
prepared using a pulsed laser deposition method, which
consists of crystalline AgCu particles embedded in amorphous
Cu films. The average particle size for the AgCu alloys was ca.
2.58 nm, and their formation was demonstrated by the shift in
the X-ray photoelectron spectroscopic (XPS) signals of Ag and
Cu, where Ag signals shifted to higher binding energy and Cu
signals shifted to lower binding energy. Maximum power
density was verified for the Ag50Cu50 alloy, ca. 86.3 mW cm−2,
and the cell voltage was 0.863 V.
Carbon nanomaterials doped with heteroatoms, such as
nitrogen, sulfur, or/and oxygen, have been found to be highly
active materials for ORR.677,717,718 The introduction of metal
ions in the synthesis of carbonaceous materials has been
essential to improve the catalytic activity of carbon materi-
als.719,720 Many examples of Cu-immobilized carbon materials,
including carbon nanotubes, graphene, and amorphous carbon,
have been used as electrocatalysts in ORR.721,722 Goenaga et al.
prepared a carbon-based catalyst by covalently attaching a
phthalocyanine-type ligand on the surface of carbon black.723
Then the ligand was used to anchor Cu2+ by exposing the
modified carbon black to a Cu2+ solution. The modified carbon
black was pyrolyzed to decompose the Cu−phthalocyanine
segment to introduce nitrogen atoms and copper ions into the
carbonaceous material.
There is evidence that Cu NPs have inherent catalytic activity
for the oxygen reduction reaction. For instance, a copper
nanocluster assembled in a colloidal solution was successfully
applied as a catalyst for ORR.724 Despite the existence of a
protective capping agent around the copper nanoclusters, the
material appears to have intrinsic activity in the electron-
transfer reaction.724 In addition, inorganic materials, such as
TiO2 or MnO2, when doped with cupper ions also showed
catalytic activity toward ORR.725,726
6.2. Reduction of CO2 to Liquid Fuels
Cu is one of the few materials that can drive the electro-
chemical reduction of CO2 in aqueous media to organic
compounds that can serve as liquid fuels, a chemical
transformation with great strategic potential for creating
renewable energy of high energy density from CO2.727 Even
though Cu displays the highest selectivity for the desired fuels,
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Figure 125. Cyclic voltammetric curves for different electrodes in an
aqueous solution of 0.25 mol/L CH3OH and 0.1 mol/L NaOH at a
scan rate of 10 mV s−1. The electrodes are indicated in the figure. SEM
images of Cu NPs used in the electrode preparation are shown.
Reprinted from ref 138. Copyright 2013 American Chemical Society.
it is difficult to translate the process to practice because of the
huge overpotential required to carry out the reduction process
and the improvement needed in its faradic yield of the desired
products at an energetically reasonable input. The faradic yield
or efficiency is the portion of the current density that is actually
used to convert the CO2 into desired products, and it accounts
for all of the possible current losses in the process. The main
hurdle of the CO2 electrochemical reduction is the competing
reaction of hydrogen evolution in aqueous media.728 At low
overpotentials, hydrogen formation overwhelms CO2 reduc-
tion; therefore, a large overpotential has to be applied to
compensate that loss. Since water works as the source of
hydrogen for the synthesis of hydrocarbons and other
compounds, the catalyst must hinder the hydrogen evolution
reaction from water as well. This is often a difficult task in CO2
reduction with H2 stemming from water.728
Li et al. have performed electrochemical CO reduction in
aqueous solution using nanocrystalline Cu, prepared by the
Figure 126. Electrodeposited nanostructured Cu foam prepared from
a 0.2 mol/L CuSO4 acidified solution with 0.5 mol/L H2SO4 at a
deposition potential of 6 V for 30 s. Reprinted with permission from
ref 708. Copyright 2014 Elsevier Ltd.
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reduction of Cu2O via two different approaches: a chemical
reduction and an electrochemical reduction.729 The two
materials were compared to an electrode prepared by casting
a commercial Cu NP solution. Figure 130 depicts the
morphological characterization of all three electrodes, which
are shown to generate important organic compounds from the
reduction of CO, including ethanol, propanol, acetate, ethylene,
and ethane. The results indicate that the grain boundary has
fundamental implications for catalytic CO reduction, and that,
using different reduction methods, oxide-derived nanocrystal-
line Cu-based nanomaterials with higher activity and enhanced
selectivity for longer carbon chain products can be obtained.
Figure 127. Scheme illustrating the growth mechanism of (A)
hierarchical Cu NWs and (B) nanothorns in Cu NWs in the presence
of ethylenediamine (EDA) and catechin. Reprinted with permission
from ref 709. Copyright 2013 Royal Society of Chemistry.
The relationship between a high catalytic effect and the
structure of grain boundaries in Cu-based electrocatalysts can
provide insights into the development of catalysts for CO2
reduction.730 Nanocrystalline Cu, composed of bare metallic
Cu NPs, prepared from the electrochemical reduction of Cu2O
layers has been used to investigate the CO2 reduction
process.731 The results indicate that the highly rough Cu
surface prepared by reducing micrometer thick Cu2O films can
achieve the reduction of CO2 to CO and HCO2H with high
faradic yields (close to 50%) at low overpotentials and that C-2
hydrocarbons can be produced at electrode potentials more
negative than −0.6 V (vs RHE).
The mechanisms that lead Cu to enable the formation of
hydrocarbons and alcohols from CO2 and the grounds for the
low overpotential are still unclear. Theoretical studies to
elucidate the mechanism of formation of hydrocarbons,
alcohols, and long-chain chemical compounds by electro-
chemical reduction of CO2 or CO using Cu and/or Cu-based
nanocatalysts have been undertaken to explain the unique
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Figure 128. TEM images of Cu NWs prepared at different
concentrations of catechin: (A) 3.0, (B) 4.5, (C) 6.0, (D) 7.49, and
(E) 14.98 mM. All samples were prepared at 80 °C for 1 h and with 13
mol/L NaOH, 8.7 mmol/L Cu2+, and 5.65 mmol/L EDA. In the inset
in (C) is presented a photograph of an individual rose stem. (F) SEM
image of Cu NWs prepared using 6 mM catechin with the
corresponding high-magnification SEM image (inset a in (F)) and a
photograph of rose stems (inset b in (F)). Reprinted with permission
from ref 709. Copyright 2013 Royal Society of Chemistry.
behavior of Cu surfaces.732−734 However, in most cases, these
efforts considered only flat surfaces, and the effect of surface
defects, quantum confinement, and grain boundaries were not
included in the calculations, which precludes a real under-
standing of the actual features and possibilities of Cu as an
electrocatalyst for synthetic photosynthesis.
The selectivity of CO2 reduction has been shown to improve
substantially using Cu-based catalysts. Ren et al. found a
Figure 129. Schematic representation of the fabrication of a Au
electrode modified with Cu NPs. Reprinted with permission from ref
713. Copyright 2013 Elsevier Ltd.
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remarkable correlation between the faradic yield of ethylene
and ethanol, two of the most important products of CO2
reduction, with the thickness of the copper oxide film as an
electrocatalyst.735 Copper oxide films with a thickness in the
range of 1.7−3.6 μm exhibited high selectivity for the C-2
products at a reducing potential of −0.99 vs RHE. Under this
condition, ethylene was the major product with a faradic yield
of 34−39%, followed by ethanol (9−16%), and methane was
formed as a minor product (less than 1%). The characterization
of the films indicated that copper oxide was reduced to metallic
particles during the CO2 reduction process; even with copper
oxide, the Cu(0) phase was claimed to be the activity site.
High selectivity for ethylene was reported for CO2 reduction
using copper nanocubes.736 A special activity of cubic crystals to
produce C-2 products was verified when the selectivity was
compared with that of polycrystalline Cu films. The catalytic
effect of copper nanocubes was compared with the activity of
crystal planes (100), (211), and (111) by single-crystal
experiments. The catalytic activities of the crystal planes in
comparison with the cube-like particles suggested that this
cubic surface structure was preferable for ethylene selectivity
compared to the close-packed (111) surface or the highly
stepped (211) surface.
6.3. Water Splitting
Copper-based nanomaterials especially as multifunctional
electrodes have been designed for both cathodic (hydrogen
evolution (HER)) and anodic (water oxidation (OER))
processes in water splitting. In the oxygen evolution reaction
(OER), the use of zerovalent copper was not possible due to
the oxidation of copper, resulting in metal corrosion.737 On the
other hand, the electrochemical potential between Cu(III) and
Cu(IV) species on the surface of a copper-based catalyst could
only be explored to drive the water oxidation process.738
Therefore, only stable metal phases must be in contact with the
electrolyte solution to hinder the metal-leaching process.739
Du et al. reported the preparation of a robust protective and
active layer on the surface of a copper substrate.738 The
deposited thin and compact film consisted of CuO with
incorporated Cu(OH)2. The formed layer prevented the
electrocorrosion of the underlying Cu substrate, allowing
sustainable catalytic water oxidation without surface degrada-
tion. A current density of 10 mA cm−2 could be obtained using
the prepared films at an overpotential of 580 mV. In addition,
the authors demonstrated that the concentrated CO32− solution
can be used as an electrolyte to prevent corrosion of the
catalyst.
An efficient oxygen evolution anode could be produced using
copper nanorods with a core/shell structure. Cheng et al.
reported a procedure for the synthesis of nanorods with a
metallic Cu core enclosed by a Cu(OH)2−CuO mixed shell.740
The samples were prepared by a sequential procedure,
consisting of an initial galvanostatic anodization of copper
foil, followed by chemical reduction using sodium borohydride,
and finally an additional galvanostatic anodization step. In the
electrochemistry test, a current density of 10 mA cm−2 was
obtained at an overpotential of 417 mV; the robustness of the
system was validated by the stable chronoamperometric curve
for a time period of 24 h.
The activity of the Cu(OH)2−CuO layer toward OER has
been demonstrated.741 Active deposited layers of Cu(OH)2−
CuO were obtained from electrochemical deposition using
Cu(II) complexes in solution as precursors, and the activity of
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the final nanomaterials was evaluated for the hydrogen
evolution reaction (HER) in weak basic media at pH 9.2.
The calculated overpotentials for HER and OER were 450 and
330 mV, respectively; assuming overpotential values for the
onset positions.
An efficient hydrogen evolution catalyst could be produced
by the (photo)electroreduction process of cuprous oxide
(Cu2O) mediated by phosphate ions;742 after the (photo)-
electroreduction, a Cu/Cu2O layer was formed. The films were
deposited on different substrates (carbon paper, fluorine-doped
tin oxide, and a molybdenum-coated glass slide), but the
adhesion of the catalyst layer to the substrate was a major
concern when the HER was performed at a high current
density. The film presented higher mechanical stability using a
molybdenum-coated glass slide. The evolution of the film
morphology and composition as a function of the (photo)-
electroreduction process is shown in Figure 131. The catalytic
activity of the obtained film is very promising with a very low
overpotential of ca. 30 mV.
Figure 130. SEM and TEM images of Cu NPs and oxide-derived Cu
electrodes. In the first row, a commercial Cu NP electrode is
presented. The second row shows an oxide-derived Cu electrode using
chemical reduction. In the third row is shown an oxide-derived Cu
electrode prepared by electrochemical reduction. The first column (a,
d, g) shows SEM images. The second column (b, e, h) and third
column (c, f, i) show low-magnification and high-resolution TEM
images. Reprinted with permission from ref 729. Copyright 2014
Nature.
The catalytic activity, higher than that of platinum, could be
obtained using a Cu-based catalyst for HER. Recently, Lu et al.
demonstrated hierarchal porous Cu−Ti as an efficient electro-
catalyst for HER.657 The activity is comparable with that of Pt/
C when the onset overpotential is considered. In fact, when the
current densities at a more negative potential were compared,
the Cu−Ti alloy was claimed to be a better catalyst than Pt/C.
Modeling studies showed that, depending on the Ti
concentration, the position of the catalytic center for HER
can be made superior to Pt as shown in a volcano plot (Figure
132).
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6.4. Cu MOFs (Metal−Organic Frameworks) as
Electrocatalysts
Combining the catalytic properties of Cu with the special
structural features of MOFs could open up interesting
possibilities in electrocatalysis.743−745 In these materials, copper
metal ions are coordinated by organic ligands, resulting in 3D
network-like structures. These Cu centers could potentially
participate in electrochemical oxidation and reduction
processes, as coordinated Cu2+ can shuttle through transient
reduced states, such as Cu+ and Cu0, or transient oxidized
states, such as Cu3+ or even Cu4+.746−750 As an example, a Cu−
bipyridine complex was the first Cu-based catalyst shown to be
highly active in water oxidation;751 a turnover frequency (TOF)
of 100 s−1 was achieved for an oxygen evolution reaction
(OER) using this complex. Chen and Meyer have demon-
strated that Cu2+ can be a robust and durable electrocatalyst for
water oxidation in neutral and or weakly basic aqueous
media.752
A composite material prepared by the deposition of a Cu-
based MOF with graphene oxide (GO) was evaluated as an
electrocatalyst by Jahan et al. The GO-incorporated Cu MOF
was tested for HER, OER, and ORR and found to possess
catalytic activity for all three reactions.753 Additionally, when
the material was tested as an electrocatalyst in a polymer
electrolyte membrane (PEM) fuel cell, a power output
equivalent to 76% of that of a commercial Pt catalyst was
obtained. The results indicate that the incorporation of the Cu-
based MOF into GO was responsible for the improvement of
its catalytic activity, selectivity, and stability during electro-
catalysis. A strong synergistic effect between the Cu MOF and
GO was discerned, suggesting that systems based on non-
precious-metal-based MOFs could be useful in electrocatalysis
if low-resistance pathways are adapted.
An electrocatalyst with enantioselective catalytic properties
can be obtained by making a Cu MOF using chiral ligands.754
Hierarchically ordered chiral structures are generated by mixing
a Cu−bipyridine complex with L-DBTA ((−)-dibenzoyl-L-
tartaric acid) or with D-DBTA ((+)-dibenzoyl-D-tartaric acid).
The ensuing supramolecular frameworks have 1D chiral
channels whose handedness is determined by the isomeric
form of dibenzoyltartaric acid used in the synthesis. The
presence of the chiral ligand L- or D-DBTA in the MOF
structure promoted the formation of a pair of homochiral
enantiomers, L-1 and D-1, which have interdigitated architec-
tures (Figure 133). The chiral 3D structure of the Cu MOF is
presented in Figure 106. The electrooxidation of small chiral
molecules was carried out to test the enantioselective
recognition capability of the L-1 and D-1 compounds, using
D- and L-malic acid and D- and L-tartaric acid. The electro-
chemical studies demonstrated a remarkable capacity for
enantioselective recognition by the L-1 and D-1 compounds,
whose activity responded to the isomerism of the substrate. L-1
exhibited a stronger electrocatalytic effect toward L-malic and
-tartaric acids, while the D-1 form exhibited greater activity
toward the D-type malic and tartaric acids.
7. GAS-PHASE CATALYSIS
As pointed out by Metzger, “The best solvent from an
ecological point of view is without a doubt no solvent”.755,756
Since the concept of sustainability has gained importance,
efficient processes dictate the use of relatively benign chemical
compounds and reduction of wastes and byproducts is
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progressively demanded.757−759 Consequently, reactions in the

gas phase can be conducted in the complete absence of solvents
or using environment-friendly solvents such as supercritical
CO2.760,761
Catalysts possessing nanostructured frameworks could
provide remarkable benefits for gas-phase reactions762 by
enabling the formation of high interfacial areas between the
catalyst and reactants.763 Nanostructured support materials
such as zeolites and mesoporous metal oxides can also prevent
aggregation of nanocatalytic species.764 Moreover, nanoporous
materials allow reactants trapped in the pores to have increased
contact time with reacting molecules and catalytically active
sites.765,766
An important insight into the catalytic effect of Cu in gas-
phase reactions was reported by Soon et al., who evaluated the
adsorption and stability of oxygen over the Cu(111) plane at
different temperatures and pressures using density functional
theory (DFT) calculations.767 These studies indicated that
oxygen does not form an adlayer on the Cu surface by Figure 131. Effect of the (photo)electroreduction on the film
chemisorptions but tends to stabilize the formation of oxidic morphology observed by SEM images (a): (i) Cu2O; (ii) +0.12 V,
species instead. Under operational conditions similar to those hν, 10 min; (iii) −0.26 V, dark, 10 min; (iv) −0.26 V, dark, 30 min.
of gas-phase reactions, the copper oxide phase was found to Current density as a function of time for the Cu2O to Cu reduction
display the highest catalytic activity and stability, suggesting that process (b). Chemical composition verified by XRD (c). Reprinted
from ref 742. Copyright 2015 American Chemical Society.
it should be the preferred phase for the development of Cu-
based nanomaterials for gas-phase reactions involving oxygen
adsorption.
This section includes some notable examples of gas-phase
catalytic reactions in which Cu nanomaterials have shown
significant activity as catalysts. In some cases Cu is present as a
zerovalent phase, but CuO is the one more frequently cited in
the literature as an intrinsic catalyst for gas-phase reactions, in
agreement with the theoretical results presented by Soon et
al.767
7.1. NOx Reduction
Strict environmental regulations that limit the amount of NOx
species emitted by burning of fuels can be satisfied by the use of
catalysts that promote the catalytic reduction of NOx in the
presence of NH3. Cu/zeolite nanostructured materials prepared
by inserting Cu ions into the zeolite structure using a simple
ion-exchange reaction with conventional zeolites can serve as
highly efficient catalysts for the selective catalytic reduction of
NOx.768−770 In fact, Baik et al. have evaluated several catalysts
and found that Cu/zeolite was the most active one for the
selective catalytic reduction of NOx.771 This catalytic activity
was ascribed to both the zeolitic structure and the exchanged Figure 132. Computational studies. (a) Proposed activity sites
Cu ions present in the zeolites. The porous structure of zeolite composed by Cu and Ti. (b) Corresponding hydrogen-binding
associated with its high surface area allows the absorption of energies of the proposed active sites in a volcano plot. (c) HER
activities and (d) exchange current densities obtained for Cu−Ti alloy
NOx and NH3 species even when these species are present in surfaces as a function of the Ti content in the alloy. Reprinted with
trace amounts in the gas phase, increasing the reactants’ permission from ref 657. Copyright 2015 Nature.
concentration on the catalyst surface. In other words, the
catalyst structure causes the confinement of the reactants and
thus promotes their catalytic conversion. The Cu/zeolite is a large-pore zeolites. Therefore, steric effects in the smaller pore
bifunctional catalyst, where tetrahedral aluminum centers act as zeolites were proposed to improve the thermal stability of the
Brønsted acid sites activating adsorbed NH3 molecules and Cu Cu/zeolite materials.
ions activate NOx molecules through a redox cycle.772,773 Habib et al. have performed the conversion of NO to N2 in
Investigations into the stability of Cu/zeolite as a nano- an O2-rich exhaust gas model using Cu-loaded Y-zeolite with
catalyst showed that its stability was directly correlated with the different Cu amounts (from 0% to 16%).775 The conversion of
zeolites’ pore sizes.774 Blakeman et al. have also examined the NO as a function of the operational temperature is depicted in
thermal stability of Cu/zeolite in studies on catalyst Figure 134. The highest NO conversion is observed with the
deactivation during thermal treatment.774 A catalyst prepared Cu/Y-zeolite having the highest Cu load, in which almost 80%
from 8-ring small-pore zeolite exhibited higher thermal stability of the NO was converted to N2 at the optimum temperature
than catalysts prepared with 10-ring medium-pore and 12-ring range of around 290 °C.
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7.2. CO Oxidation
Cu-based nanomaterials have been employed in the catalytic
oxidation of CO to CO2776,777a process often used in the
exhaust systems of automobiles to reduce CO emission into the
atmosphere.778 The catalytic oxidation of CO is also important
in the context of CO removal from H2 produced by steam
reforming of organic compounds, such as methanol or
methane:779 the presence of trace amounts of CO in H2 can
be detrimental to the steam reforming process because the use
of H2 in hydrogenation processes or fuel cells involves noble-
metal catalysts that are poisoned by modest amounts of CO.
Zhou et al. have demonstrated the synthesis of CuO
nanocrystals with different shapes, including CuO NPs,
nanobelts, and nanoplatelets, prepared by precipitation
methods (Figure 135).780 All forms of these CuO nanocrystals
were tested as catalysts for the conversion of CO to CO2,
revealing a direct relationship between the catalytic reactivity of
the CuO nanostructures and the exposed crystal planes, which
vary with the crystal shape. The specific reaction rate was
highest for CuO nanoplatelets, followed by nanobelts and NPs;
the former achieved a specific reaction rate 6-fold higher than
that of CuO nanobelts. On the basis of this huge performance
differential, it has been proposed that the (011) crystal planes
are the most active as they are the predominant exposed planes
in the CuO nanoplatelets.
The expected improved catalytic activity of porous catalysts
vs solid catalysts in gas-phase catalytic oxidation of CO was
demonstrated by Zhou et al.781 In this study, various structural
forms of CuO, including microflowers, microspheres, and
porous microstructures, were prepared by carbonate-assisted
hydrothermal synthesis. The Brunauer−Emmett−Teller (BET)
surface area of the synthesized porous CuO structure was found
to be 30 m2/g, and the specific reaction rate was more than 6-
fold higher for the porous CuO than other CuO solid particles
(Figure 136).
Svintsitskiy et al. have utilized both in situ and operando
techniques to correlate the catalytic activity of CuO nano-
powders as a function of the surface composition of the metal
oxide.782 Figure 137 depicts the CO consumption as a function
of the surface composition of a CuO nanopowder at different
temperatures. A temperature-programmed reaction (TPR)
demonstrated that CO oxidation could be carried out at low Figure 133. Chiral 3D structure of a Cu MOF (a, b) with two different
temperature, and a shoulder corresponding to the conversion of types of nanochannels along the a axes (c). Reprinted with permission
CO can be seen at temperatures ranging from 60 to 135 °C on from ref 754. Copyright 2014 Elsevier Ltd.
the graph. In this temperature range, the catalytic activity was
associated with the metastable phase Cu4O3 on the surface of The use of mesoporous CuO as a catalyst could be an
the CuO nanopowder. efficient approach to CO oxidation, mainly because Cu is an
Mesoporous CuO with unique nanowalnut-shaped particles abundant and cheaper material in comparison to the
and a one-dimensional pore structure possessing a surface area alternatives that are based on noble metals, with particular
of around 60 m2/g was found to be quite effective for CO reference to Au.784−786 However, as reported by Chung et al.,
oxidation. Yu et al. have developed a wet chemistry protocol extraordinary catalytic activity was observed for CuO/CeO2
that produces porous CuO nanoribbons and nanowalnuts materials, prepared by coprecipitation of nitrates at various pH
(Figure 138).783 The effect of the surface area and pore size on values.787 The materials prepared at pH values above 12
the catalytic performance could be verified by analyzing the showed the highest activity for CO oxidation. In the best case,
data presented in Table 9. The CuO nanowalnuts’ catalytic 99% conversion with 88% selectivity for CO was observed for
activity was found to be 23 times higher than that of the reactions conducted at 125 °C. The outstanding catalytic
commercial CuO NPs, which had an average particle diameter activity of catalysts based on CuO/CeO2 has been attributed to
of 40 nm. The higher surface area of the CuO nanowalnuts interfacial regions between the CuO and CeO2 domains
cannot by itself explain their enhanced catalytic activity relative (Figure 139).788 The synergistic interaction between CuO and
to that of CuO nanobelts. Interestingly, the nanowalnuts’ CeO2 is due to the ability of the CeO2 phase to store and
surface area is 3 times higher than that of CuO nanoribbons, release oxygen atoms via a redox process, along with the
but their catalytic activity is 16 times higher. presence of a special CuO−CO interaction. In fact, the oxygen
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storage/release ability of CeO2 is intensified in the presence of
CuO. The CO molecules adsorb on the CuO surface, and the
adsorbed molecules migrate to the interfacial region with the
CeO2 oxide. The O2 is then added to the interface passing
through the oxygen vacancies on the CeO2 phase.
The intriguing activity of the CeO2 and CuO interface has
been further investigated by Yang et al. in nonstoichiometric
Ce1−xCuxO2−δ-supported Cu catalysts,789 which displayed a
superior catalytic performance for CuO/Ce0.978Cu0.022O2−δ for
the oxidation of Co in a H2-rich environment. The catalyst can
promote nearly 100% conversion of CO at 115 °C, in the gas
mixture, which is the lowest temperature for total CO
conversion reported in the literature. In addition, superior
catalytic activity is also claimed due to its selective promotion of
CO oxidation in the presence of H2. CuO/Ce0.978Cu0.022O2−δ
achieved 100% selectivity for the conversion of O2 to CO2 at
115 °C. The observed results were justified by the increase in
the oxygen vacancies in the CeO2 phase due to the inclusion of
Cu2+ ions. The conversion of CO increased with the
temperature, while the opposite behavior was observed for
the selectivity (Figure 140). At low temperature, nearly 100%
selectivity was achieved, while, at high temperature, the
oxidation of hydrogen occurred.
7.3. Water−Gas Shift Reaction
H2 is an important gas in the chemical industry, as it is used for
the production of ammonia and numerous other hydrogenation
products.790 In addition, H2 can be used as a fuel since it has a
high energy density (∼143 MJ/kg) based on its combustion.
Hydrogen could be a clean alternative fuel whose use would
reduce anthropogenic emissions of pollutants into the
condition.794 The path mediated by the COOH intermediate
has been advocated over the redox pathway (Figure 141). The
ZrO2 support can indeed intensify the reactivity of Cu to
catalyze the WGS reaction by inducing positive changes on Cu
sites at the interface between Cu and ZrO2 where the water
dissociation barrier was reduced to 0.55 eV. The predominance
Figure 135. TEM images of (a) CuO NPs, (b) CuO nanobelts, and
(c) CuO nanoplatelets. Reprinted with permission from ref 780.
Copyright 2006 IOP Publishing.
of the COOH intermediate was also highlighted in studies
using only the Cu(111) surface plane as the catalyst.795
The catalytic effect, mainly attributed to the Cu surface, is in
agreement with the experimental work published by Saito et al.
when they investigated the effect of pretreatment over the
catalytic activity of Cu/ZnO/Al2O3 and Cu/ZnO/ZrO2/Al2O3
catalysts;796 the catalytic activity of the catalyst toward the
WGS reaction was mainly correlated with the Cu surface area.
The WGS reaction was also studied using in situ ambient-
pressure XPS over metal−oxide interfaces.797 In the case of
CeOx/Cu(111), the most abundant species under WGS
reaction conditions on the Cu(111) surface was adsorbed
CO, an experimental finding that is consistent with the
computational studies which concluded that the COOH
pathway was dominant.
The activity of Cu surfaces and oxide-supported Cu NPs
clearly revealed an enhanced catalytic effect in Cu NPs
supported on oxide phases.798 The activation energy for a flat
Cu foil is 15.2 kcal/mol, and the activation energy for a rough
Cu foil surface is 13.7 kcal/mol, demonstrating the effect of

Figure 134. Conversion of NO as a function of temperature catalyzed

by Cu/Y-zeolite with different Cu loads. Reprinted from ref 775.
Copyright 2014 American Chemical Society.

atmosphere791 and could initiate a “hydrogen economy” era.

However, to achieve this, more viable synthetic processes and
more efficient catalysts are required.99,100 The water−gas shift
(WGS) reaction (H2O + CO → H2 + CO2) is an attractive
approach for H2 production792 as it could be performed using
oxide-supported Cu nanomaterials, in which intense synergistic
effects between Cu and the oxide support have been
observed.793 Tang et al. investigated the WGS reaction over a
binary model Cu/ZrO2 using first-principles calculations and
found that ZrO2 does not participate in the reaction since water Figure 136. Specific conversion rate of CO over CuO catalysts with
molecules easily dissociate at interfacial sites and these species different particle structures at 110 °C. Reprinted with permission from
are not susceptible to be removed by CO in the reaction ref 781. Copyright 2010 Wiley-VCH Verlag GmbH & Co. KGaA.

3785 DOI: 10.1021/acs.chemrev.5b00482

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Chemical Reviews Review

roughness on the catalytic activity. The observed activation 8. CONCLUSIONS AND FUTURE SCOPE
energy for Cu NPs supported on MgO was 13.8 kcal/mol, a This review has highlighted recent advances in methods for the
preparation of Cu and Cu-based NPs and their applications in
value similar to that observed for the rough Cu surface. The
different types of catalysis. These protocols make it possible to
control the size, shape, and morphology of the nanosystems,
which is of paramount importance in the design and the
development of Cu NPs with specific properties tailored to
applications in catalysis ranging from organic transformations
to electrocatalysis, photocatalysis, and so on. The synthetic
section provided an overview of important procedures for the
preparation and characterization of Cu and Cu-based NPs,
including wet chemical, reverse micelle, and sophisticated
protocols involving sonochemistry, microwaves, photo- and
electrochemistry. Preparative procedures for supported Cu
NPs, other Cu-based NPs, the growth mechanism of Cu NPs,
Figure 137. Temperature-programmed reaction (TPR) for CO and a brief description of characterization were also presented.
consumption as a function of the surface composition of a CuO In addition, reports on the applications of various Cu
nanopowder at different temperatures. Reprinted from ref 782.
Copyright 2013 American Chemical Society.
nanocatalysts for a wide range of organic reactions such as
alkyne−azide cycloaddition, reduction, coupling (including A3,
catalytic activity was higher in Cu/CeO2 and Cu/TiO2, which
had observed activation energies in the range of 7−9 kcal/mol.
Cu NPs deposited on TiO2 have been excellent catalysts for
the WGS reaction, with an observed activation energy of 8.3
kcal/mol.799 Figure 142 depicts scanning tunneling microscopy
(STM) images of Cu NPs on TiO2, which indicate that
different particle sizes are formed on the surface of TiO2, from
1 nm (in the case of lower amounts of Cu deposited) to 3.2 nm Figure 139. Model used to explain CO oxidation over CuO/CeO2
(for larger deposited quantities). Different samples with varying catalysts. Reprinted from ref 788. Copyright 2010 American Chemical
degrees of admetal coverage were prepared; their activity Society.
toward the WGS reaction increased with their Cu coverage up
to a maximum of 0.3 monolayer (ML). Further increases in Cu
coverage beyond this limit caused the catalytic activity of the homocoupling, Sonogashira, C−S coupling, etc.), arylation (O-
samples to decrease. arylations, N-arylation, C−H arylation), oxidation, multi-
component “one-pot” synthesis, and miscellaneous reactions
were discussed.
Although there have been important developments in the
preparation of earth-abundant Cu-based NPs in terms of the
diversity of structures that can be obtained, the reactions they
can undergo, and the selectivity they can achieve, many
challenges still remain to be addressed. In particular, over-
coming the limited stability of Cu NPs and their tendency to
Figure 138. (a) TEM and (b) HRTEM images CuO particles with a experience leaching (particularly under harsh conditions such as
nanowalnut shape. Reprinted with permission from ref 783. Copyright high temperature/pressure) will be necessary. The design of
2012 Royal Society of Chemistry. newer and novel Cu NPs and the development of practical and
cost-effective methods for the synthesis of more stable Cu NPs
(featuring robust interactions based on strong ionic and
covalent bonding between the support and Cu) are still
needed to overcome such problems.
Toward this end, there are some ongoing efforts to design
polymer-embedded copper nanocatalysts for continuous-flow
Table 9. BET Surface Area, Particle Size, and Catalytic reactions. The combination of Cu with other metals could
Performance of Different CuO NPs provide new and better catalysts for various chemical
transformations: combinations of two separate metals may be
catalytic performance more effective than either alone. This concept has been applied
(mL h−1 g−1)
in a continuous-flow Pd−Cu dual reactor, for instance, where
BET surface particle Pd and Cu act as cooperative catalysts for Sonogashira C−C
area (m2/g) size (nm) 50 °C 100 °C 150 °C
coupling reactions.800 We envisage that newer candidates
CuO 61.24 8 160 133.26 137.26
nanowalnuts (particularly hybrid ones) will be coupled with Cu to perform
CuO porous 21.93 22 9.52 8.52 11.46 such important reactions on large scales.
nanoribbons Recent developments in the burgeoning field of Cu-
commercial 0.28 40 6.75 7.38 8.15 containing photocatalytic systems and Cu-based nanomaterials
CuO NPs have also been reviewed. Particular attention was paid to the
3786 DOI: 10.1021/acs.chemrev.5b00482
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Chemical Reviews
Figure 140. (a) Conversion of CO and (b) reaction selectivity as a
function of the temperature over different CuO/CeO2 catalysts
containing different amounts of Cu2+ added to the CeO2 phase.
Reprinted with permission from ref 789. Copyright 2014 Elsevier Ltd.
functions and properties of Cu and Cu-based nanomaterials in
photocatalytic reactions. Despite much advancement in this
area, as outlined above, there are still several difficulties that
limit the wider usage of Cu-based nanomaterials. The first of
these is the difficulty of achieving precise structural control of
the Cu and Cu-based nanomaterials, which is an essential
prerequisite for the establishment of shape-, size-, or defect-
dependent properties of the materials and the optimization of
the materials’ functions. Second, there is still room for careful
and rigorous characterization of Cu-containing nanomaterials
under various reaction conditions. Cu nanomaterials have a
wide range of potential applications, notably in photocatalysis.
However, the structural transformations occurring during
photocatalytic reaction conditions may require special
attention, as discussed above. In other words, it is prudent to
characterize the materials after photocatalytic reactions and
then compare the results with those obtained for the as-
3787
Review
Figure 141. Representation of the competing pathways for the water−
gas shift reaction over a Cu/ZrO2 system. Reprinted from ref 794.
Copyright 2010 American Chemical Society.
prepared materials to precisely elucidate and identify the active
catalytic sites; in situ observation of the possible structural
variation of the Cu species during catalytic processes would be
ideal. Finally, there is a need for deeper understanding of the
functions/mechanism of the Cu species in photocatalysis
systems: most of the existing theories concerning the functions
of Cu nanomaterials in any given photocatalytic system are
somewhat speculative. This, therefore, calls for more research
into the mechanistic aspects of Cu-containing photocatalytic
systems by physicochemical and theoretical methods.
Interest in Cu-based nanomaterials as electrocatalysts has
increased because Cu exhibits many unique features that are
not seen in many other metals. It is evident that the
development of feasible electrochemical processes using Cu
as an electrocatalyst will mainly hinge on overcoming the large
overpotentials and low current densities associated with the
electrochemical process. The use of Cu in the form of
nanostructures is definitely an excellent approach for increasing
the surface energy of active sites on Cu surfaces and reducing
overpotentials. In addition, hybrid materials composed of Cu
nanomaterials on conducting materials are promising electro-
catalysts. The conducting materials could work as low-
resistance electron pathways to avoid charge buildup on the
Cu NPs, thereby controlling the band levels of Cu and helping
to reduce the reaction’s overpotential.
As observed in many of the studies presented here, the effect
of the porosity on gas-phase catalysts is too important to be left
unattended in the development of more efficient Cu-based
systems. The design of highly porous materials containing Cu
domains spread out over the surface is promising in this field.
In addition, the association of support materials that interact
synergistically with Cu will be important for increasing its
catalytic activity in gas-phase reactions. This has been
demonstrated by the association of Cu with zeolites and
CeO2, which resulted in the identification of interesting
alternative Cu-based nanocatalysts for gas-phase reactions.
The importance of process scalability for the preparation of
desirable materials using Cu NPs on a commercial scale should
not be underestimated. In this regard a continuous-flow Cu
reactor or continuous-flow bimetallic reactors will hopefully
offer advantages over conventional methods. Ongoing progress
in the development of Cu and copper-based NPs will offer a
wide range of useful options in heterogeneous catalysis/
nanocatalysis, benign sustainable protocols, and cost-effective
methods in the near future. It is hoped that this review will play
some imperative and stimulating role in helping shape future
developments in this important field.
DOI: 10.1021/acs.chemrev.5b00482
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Chemical Reviews
Figure 142. STM images of Cu NPs deposited on the (110) crystal
plane of TiO2 at different levels of Cu coverage and sample
temperatures: (a) 0.1 ML of Cu at 298 K, (b) 0.1 ML of Cu after
annealing at 625 K for 10 min, (c) 2.3 ML of Cu at 298 K, and (d) 2.3
ML of Cu after annealing at 625 K for 10 min. Cu was deposited at
298 K, and all STM images were obtained at 298 K (2.5 V, 0.05 nA)
with a size of 150 × 150 nm. Reprinted from ref 799. Copyright 2009
American Chemical Society.
AUTHOR INFORMATION
Corresponding Authors
*E-mail: manoj.gawande@upol.cz.
*E-mail: radek.zboril@upol.cz.
*E-mail: varma.rajender@epa.gov; rajvarma@hotmail.com.
Notes
The authors declare no competing financial interest.
Biographies
Manoj B. Gawande received his Ph.D. degree in chemistry in 2008
from the Department of Chemistry, Institute of Chemical Technology
(formerly the University Department of Chemical Technology
(UDCT)), Matunga, Mumbai, India, with Prof. R. V. Jayaram. After
several research stints in Germany, South Korea, Portugal, Singapore,
and England, recently, he worked as a visiting professor/scientist with
Prof. Dunwei Wang, Boston College, Boston, MA, and Prof. Rajender
S. Varma at the Environmental Protection Agency (EPA), Cincinnati,
OH. Presently, he is working as a senior researcher and the head of the
Nanocatalysis Research laboratories at the Regional Centre of
Advanced Technologies and Materials (RCPTM), Faculty of Science,
Palacky University, Olomouc, Czech Republic. His research interests
include nanocatalysis and advanced nanomaterials and their
applications. He has published over 70 scientific publications,
including reviews, patents, editorials, and articles. He is currently
supervising several doctoral students and postdoctoral workers.
Anandarup Goswami, born in Kalna, near Kolkata, India, completed
his B.Sc. (Hons.) in 2002 from Presidency College, Kolkata, and M.Sc.
in 2004 from the Indian Institute of Technology, Kanpur. He obtained
a Ph.D. in organolithium chemistry under Prof. David B. Collum
(2010) and later joined Prof. Kai C. Hultzsch’s group at Rutgers
University to work on organometallic catalysis. He has a keen interest
in heterogeneous catalysis, which he explored in Prof. Tewodros
(Teddy) Asefa’s group, with special emphasis on silica-based materials.
3788
Review
Presently, he is working as a researcher at the Regional Centre of
Advanced Technologies and Materials, Faculty of Science, Palacky
University, Olomouc, Czech Republic, with Dr. Manoj B. Gawande
and Prof. Radek Zboril.
François-Xavier Felpin was born in Villefranche-sur-Saône, France, in
1977. He received his Ph.D degree in 2003 from the University of
Nantes under the supervision of Professor Jacques Lebreton working
on the synthesis of alkaloids. After receiving his Ph.D., he was engaged
in a postdoctoral position with Professor Robert S. Coleman at The
Ohio State University working on the synthesis of mitomycin. In 2004,
he joined the University of Bordeaux as an assistant professor and
received his habilitation in 2009. In the fall of 2011, he moved to the
University of Nantes, where he was promoted to full professor. Prof.
Felpin is a junior member of the Institut Universitaire de France, and
he recently received the 2014 Young Researcher Award from the
French Chemical Society. His research interests include heterogeneous
and homogeneous sustainable catalysis, new technologies, and material
chemistry.
Tewodros (Teddy) Asefa is currently a professor in the Department of
Chemistry and Chemical Biology and the Department of Chemical
and Biochemical Engineering at Rutgers University in New Brunswick,
NJ. He is also a member of the Rutgers Institute for Materials, Devices,
and Nanotechnology (IAMDN) and the Rutgers Energy Institute
(REI). In December 2009, he helped to put together the Rutgers
Catalysis Research Center (RCRC). His group at Rutgers is involved
in the development of synthetic methods of a wide array of functional
and core/shell nanomaterials and the investigation of their potential
applications in catalysis, electrocatalysis, targeted delivery of drugs to
specific cells, nanocytotoxicity, solar cells, and environmental
remediation. He is a recipient of the National Science Foundation
(NSF) CAREER Award (2007−2012), the NSF Special Creativity
Award in 2011, the Rutgers Board of Governors Research Fellowship
in 2012, and multiple federal and local research grants. He was named
the National Science Foundation American Competitiveness Fellow
(NSF ACIF) in 2010 and also serves as a panelist for several federal
and international agencies. He has recently coedited a book on
nanocatalysis (Wiley) and has written over 120 peer-reviewed
scientific papers and several book chapters over the past decade.
Xiaoxi Huang was born in China. He received a B.S. degree in
pharmaceutical science (2011) from the Peking University Health
Science Center. He is now a Ph.D candidate in the Department of
Chemistry and Chemical Biology, Rutgers University, under the
supervision of Prof. Tewodros (Teddy) Asefa. His current research
interests include the design and synthesis of novel multifunctional
nanomaterials for biomedical and catalysis applications.
Rafael Silva, born in Brazil in 1984, received his B.Sc. degree in
chemistry from Maringá State University (Brazil) in 2006, where he
also obtained his M.Sc degree in chemistry in 2008. During his M.Sc.
studies, he worked on surface chemistry, developing synthetic methods
for the chemical modification of polyethylene surfaces. He obtained his
Ph.D. degree in chemistry from Rutgers University (United States) in
2013 working on the design and synthesis of functional nanomaterials
for nanomedicine and eletrocatalysis. He is currently a professor in the
Department of Chemistry at Maringá State University, and his current
research focuses on the development of electrocatalysts for use in
renewable energy technologies. He has authored more than 25 papers
and 2 book chapters and filed 3 patents in the areas of nanomaterials,
surface chemistry, and catalysis.
Xiaoxin Zou was awarded a Ph.D. in inorganic chemistry from Jilin
University, China, in June 2011, and then moved to the University of
California, Riverside, and then Rutgers, The State University of New
DOI: 10.1021/acs.chemrev.5b00482
Chem. Rev. 2016, 116, 3722−3811
Chemical Reviews Review

Jersey, as a postdoctoral scholar from July 2011 to October 2013. He is BF-TEM bright-field transmission electron micros-
currently an associate professor in the State Key Laboratory of copy
Inorganic Synthesis and Preparative Chemistry at Jilin University. His BMIM+BF4− 1-butyl-3-methylimidazolium tetrafluoro-
research interests focus on the design and synthesis of noble-metal- borate
free, nanostructured, and/or nanoporous materials for water splitting BMIM+PF6− 1-butyl-3-methylimidazolium hexafluoro-
and renewable energy applications. phosphate
Radek Zboril received his Ph.D. degree at the Palacky University, Brij 30 CH3(CH2)10CH2(OCH2CH2)4OH
Olomouc. After his Ph.D. studies, he took positions at the Universities Brij 56 CH3(CH2)14CH2(OCH2CH2)10OH
of Tokyo, Delaware, and Johannesburg. Currently, he is a professor in n-Bu4POAc tetrabutylphosphonium acetate
the Department of Physical Chemistry and a general director of the [C2OHmim][NTf2] 1-ethyl-3-methylimidazolium bis-
Regional Centre of Advanced Technologies and Materials at Palacky (trifluoromethylsulfonyl)imide
University, Olomouc. His research interests are centered on CB conduction band
nanomaterials, including iron- and iron oxide-based NPs, silver NPs, CTAB cetyltrimethylammonium bromide
carbon nanostructures, and magnetic NPs, and encompass their CTAC cetyltrimethylammonium chloride
synthesis, physicochemical characterization, and applications in Cu copper
catalysis, water treatment, antimicrobial treatment, medicine, and Cu NPs copper nanoparticles
biotechnology. He has published more than 250 scientific papers, Cu(AOT)2 copper dioctyl sulfosuccinate
including 10 review papers in American Chemical Society (ACS) CuMSC Cu−mesoporous silicate catalyst
journals (e.g., Chemical Reviews, Accounts of Chemical Research, ACS CVD chemical vapor deposition
Nano). DBD dielectric battery discharge
D-DBTA (+)-dibenzoyl-D-tartaric acid
Rajender S. Varma was born in India (Ph.D., Delhi University, 1976). DBSA dodecylbenzenesulfonic acid sodium salt
After postdoctoral research at Robert Robinson Laboratories, DFT density functional theory
Liverpool, U.K., he was a faculty member of the Baylor College of DH diamond nanoparticles
Medicine and Sam Houston State University prior to joining the diglyme 1-methoxy-2-(2-methoxyethoxy)ethane
Sustainable Technology Division at the U.S. Environmental Protection DLS dynamic light scattering
Agency in 1999. He has over 40 years of research experience in DMAc N,N-dimethylacetamide
management of multidisciplinary technical programs and is extensively DMF N,N-dimethylformamide
involved in sustainable aspects of chemistry, which include develop- DMFC direct methanol fuel cell
ment of environmentally benign synthetic methods using alternate DMO dimethyl oxalate
energy input using microwaves, ultrasound, and mechanochemistry, DMSO dimethyl sulfoxide
etc., efficient technologies for greener remediation of contaminants, DTBB 4,4′-di-tert-butylbiphenyl
and environmental sciences. Lately, he has been focused on greener EDA ethylenediamine
approaches to assembly of nanomaterials and sustainable applications EDS energy-dispersive X-ray spectroscopy
of magnetically retrievable nanocatalysts in benign media. He is a EG ethylene glycol
member of the editorial advisory board of several international journals EMIM+BF4− 1-ethyl-3-methylimidazolium tetrafluoro-
and has published over 430 scientific papers and been awarded 14 U.S. borate
patents. EMIM+PF6− 1-ethyl-3-methylimidazolium hexafluoro-
phosphate
ACKNOWLEDGMENTS fcc face-centered cubic
We gratefully acknowledge the support from the Operational GC gas chromatography
Program Research and Development for InnovationsEuro- GO graphene oxide
pean Regional Development Fund (Project CZ.1.05/2.1.00/ HAADF-STEM high-angle annular dark-field scanning
03.0058) and the Operational Program Education for transmission electron microscopy
CompetitivenessEuropean Social Fund (Project CZ.1.07/ HER hydrogen evolution reaction
2.3.00/30.0041) of the Ministry of Education, Youth and HOMO highest occupied molecular orbital
Sports of the Czech Republic. T.A. gratefully acknowledges HRTEM high-resolution transmission electron mi-
financial support from the U.S. National Science Foundation croscopy
(NSF) for his group’s work in catalysis and electrocatalysis over HT hydrotalcite
the past several years. ICP-AES inductively coupled plasma atomic emis-
sion spectroscopy
ABBREVIATIONS ICP-MS inductively coupled plasma mass spec-
1,2-BDO 1,2-butanediol trometry
1,2-PDO 1,2-propanediol Ida iminodiacetate
4-NP 4-nitrophenol IHOAM model incipient hydrous oxide/adatom mediator
AAS atomic absorption spectroscopy model
AB ammonia−borane IL ionic liquid
acac acetylacetonate ImAc immobilized metal affinity chromatogra-
ALD atomic layer deposition phy
AlO(OH) aluminum oxyhydroxide IPA isopropyl alcohol
AOT dioctyl sodium sulfosuccinate L-DBTA (−)-dibenzoyl-L-tartaric acid
BCFs bacterial cellulose nanofibers LMB leucomethylene blue
BET Brunauer−Emmett−Teller LUMO lowest unoccupied molecular orbital

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Chemical Reviews Review

MB methylene blue WLHSV weight liquid hourly space velocity

MCM-41 Mobil composition of matter no. 41 XPS X-ray photoelectron spectroscopy
MCR multicomponent reaction XRD X-ray diffraction
MG methylene glycol
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3811 DOI: 10.1021/acs.chemrev.5b00482

Chem. Rev. 2016, 116, 3722−3811