Chem Soc Rev

View Article Online

TUTORIAL REVIEW View Journal | View Issue
Published on 18 May 2017. Downloaded by Indian Institute of Technology - Jammu on 7/13/2023 8:55:06 AM.

Controllable design of tunable nanostructures

inside metal–organic frameworks
Cite this: Chem. Soc. Rev., 2017,
46, 4614 a
Liyu Chen, Rafael Luque *b and Yingwei Li *a

Received 15th July 2016
DOI: 10.1039/c6cs00537c
rsc.li/chem-soc-rev
The controllable encapsulation of nanoentities (such as metal nanoparticles, quantum dots, poly-
oxometalates, organic and metallorganic molecules, biomacromolecules, and metal–organic polyhedra)
into metal–organic frameworks (MOFs) to form composite materials has attracted significant research
interest in a variety of fields. These composite materials not only exhibit the properties of both the
nanoentities and the MOFs but also display unique and synergistic functionalities. Tuning the sizes, com-
positions, and shapes of nanoentities encapsulated in MOFs enables the final composites to exhibit
superior performance to those of the separate constituents for various applications. In this tutorial review
article, we summarized the state-of-the-art development of MOFs containing encapsulated tunable
nanoentities, with special emphasis on the preparation and synergistic properties of these composites.

Key learning points

 Advantages and challenges of employing MOFs as hosts for nanoentities (NEs).
 General strategies for the encapsulation of NEs in MOFs.
 Understanding the key requirements for controllable encapsulation of NEs inside MOFs.
 Synergistic functionalities of MOF-encapsulated NEs.
 Future challenges and opportunities in the field of MOF-encapsulated NEs.

1. Introduction
Nanoentities (NEs), which are entities with at least one nano-
scale dimension, exhibit unique physical and chemical proper-
ties that differ from those of their bulk counterparts.1 Over the
last two decades, significant advances in nanoscience and nano-
technology have enabled the rational synthesis of NEs with
tunable sizes, compositions, and shapes. This success has in
turn enabled the design of nanostructures that have tunable
properties and show promise for use in fields such as catalysis,
optics, electronics, and magnetic materials.
Owing to increasing interest in sustainable chemistry, much
effort has been devoted to fabricating industrially applicable
composites that consist of functional NEs encapsulated in porous
host materials such as carbonaceous materials, mesoporous
silica, metal oxides, and polymers. These porous materials allow
a
State Key Laboratory of Pulp and Paper Engineering, School of Chemistry and
Chemical Engineering, South China University of Technology, Guangzhou 510640,
China. E-mail: liyw@scut.edu.cn
b
Departamento de Quı́mica Orgánica, Facultad de Ciencias, Universidad de Córdoba,
Edificio Marie Curie (C-3), Campus de Rabanales, Ctra. Nnal. IV-A, Km 396,
E14014, Cordoba, Spain. E-mail: q62alsor@uco.es
chemical species free access to the embedded NEs and prevent
aggregation of the NEs, which thereby enhances their stability.
Furthermore, the host materials can provide additional active
sites to work synergistically with the encapsulated NEs so that the
composite materials can exhibit properties that differ from those
of their constituents. The enhanced performance of these
composites with respect to that of the separate constituents
has inspired the search for new classes of porous materials to
serve as hosts.
One such new class comprises porous crystalline materials
known as metal–organic frameworks (MOFs) or porous coordi-
nation polymers, which consist of metal ions or clusters that
are connected by organic linkers2,3 and feature well-defined pore
structures, large surface areas, and structural flexibility. These
properties make MOFs appropriate hosts for active phases with
various applications. The encapsulation of nano-sized guests,
such as metal nanoparticles (NPs), quantum dots (QDs), poly-
oxometalates (POMs), organic and metallorganic molecules,
biomacromolecules, and metal–organic polyhedra, in MOFs has
led to the development of new functional materials for applica-
tions such as gas adsorption and storage, sensing, heterogeneous
catalysis, and molecular release systems. Several reviews of the
use of MOFs as supports for NEs and the applications of the

4614 | Chem. Soc. Rev., 2017, 46, 4614--4630 This journal is © The Royal Society of Chemistry 2017
 View Article Online

Tutorial Review Chem Soc Rev

resulting composite materials have been published.4,5 How-
ever, there have been no tutorial reviews of recent work on the
encapsulation of NEs in MOFs in such a way that the locations,
sizes, compositions, and shapes of NEs can be controlled to
provide significantly enhanced properties in comparison to
those of their individual counterparts. Methods of achieving
Published on 18 May 2017. Downloaded by Indian Institute of Technology - Jammu on 7/13/2023 8:55:06 AM.
2. MOFs as hosts for NEs
2.1 Benefits
MOFs are constructed from bridging organic linkers (e.g., carboxyl-
ates, phosphonates, sulfonates, and heterocyclic compounds)
and inorganic secondary building units (SBUs). Ideally, by the
judicious selection of SBUs and linkers, the pore sizes, shapes,

such control are still in their infancy, and a review of what has
been accomplished to date is essential for scientists interested and functionalities of the resulting MOF matrices can be tuned.
in working in this emerging area or in nanomaterials design Compared with traditional porous materials such as zeolites
in general. and carbon, MOFs have several unique properties that are not
In this tutorial review, we begin by discussing the advan- shared by traditional porous materials such as zeolites and
tages and limitations of MOFs as host materials with respect to carbon. MOFs are thus ideal platforms for the encapsulation of
other kinds of porous materials. Subsequently, we compare many different functional guests. These properties are discussed
state-of-the-art strategies for the preparation of MOF-encapsulated in the following subsections.
NEs. Various reported NE@MOF composites with well-defined 2.1.1 Tunable pore environments. The inner pore surfaces
dispersities, sizes, compositions, and shapes are then presented of MOFs can be precisely functionalized or modified in another
(Fig. 1), and the superior performance of such hybrid composites way, either directly or by post-assembly modification. Isostruc-
for various applications is discussed. Finally, we address the tural MOFs can be synthesized by replacing the metal ions in
challenges that must be overcome if NE@MOF composites are the inorganic SBUs with other metal ions or by functionalizing
to find practical applications. the organic linkers. In this way, MOFs with identical structures
but distinctive functionalities can be made and used to study
how the chemical environment in the pores affects the perfor-
mance of the encapsulated guest species.
For example, Huang et al. encapsulated Pd NPs in isoreticular
Liyu Chen received his bachelor’s (having the same topology) MOFs with differently functionalized
degree in chemistry from South organic linkers (Pd@UiO-66-X, where X = H, NH2, or OMe) to
China University of Technology in determine how the donation of electrons from the functionality
2013, after which he started his in the linker affects the performance of the embedded Pd NPs.6
doctoral work under the super- These investigators found that Pd@UiO-66-NH2 catalysts dis-
vision of Professor Li at the same played weaker oxidation capability than Pd@UiO-66-OMe cata-
university. His research is centered lysts and thus exhibited higher selectivity for the acetal product
on the design and preparation of (rather than the ester) in the aerobic reaction between benzalde-
MOF-encapsulated metal nano- hyde and ethylene glycol. The weaker oxidation capability of
structures and their applications Pd@UiO-66-NH2 was attributed to an increase in electron density
in heterogeneous catalysis. on the Pd surface as a result of NH2–Pd interactions.
2.1.2 Tunable pore size. Isoreticular MOFs with various
Liyu Chen pore sizes can be prepared, which has not been achieved with

Rafael Luque (Departamento de Yingwei Li received his BS degree

Quimica Organica, Universidad de
Cordoba, Spain) has published
more than 270 peer-reviewed
papers. He is an Editorial/Advisory
Board member of Chemical
Society Reviews, Green Chemistry,
ChemCatChem, Topics in Current
Chemistry and Scientific Reports,
as well as Editor of Journal of
Molecular Catalysis A: Chemical.
He has received several awards,
Rafael Luque including a Green Talents award
from BMBF, Germany, a TR35
Spain award from Technology Review and MIT and an RSC
Environment, Sustainability and Energy Early Career Award
from the RSC.
in 1998 and his PhD in 2003,
both from the Department of
Chemistry of Tsinghua University,
and he then conducted postdoctoral
work at the University of Calgary
and the University of Michigan
(Ann Arbor) from 2003 to 2007.
He is currently a full professor
at the School of Chemistry and
Chemical Engineering, South China
University of Technology. His
Yingwei Li research focuses on the design
and synthesis of new metal–organic
framework materials for heterogeneous catalysis and gas adsorption
and separation. He has published more than 100 papers in the peer-
reviewed literature.

This journal is © The Royal Society of Chemistry 2017 Chem. Soc. Rev., 2017, 46, 4614--4630 | 4615

Chem Soc Rev
Published on 18 May 2017. Downloaded by Indian Institute of Technology - Jammu on 7/13/2023 8:55:06 AM.
Fig. 1 MOFs function as versatile hosts for the encapsulation of NEs. NE@MOF composites can be placed in four categories on the basis of their
structural characteristics: (1) within-the-pore structures, (2) core–shell structures, (3) yolk–shell structures, and (4) sandwich structures.
other solid materials. By increasing the length of the organic
linker, a series of MOFs with increasingly large pore apertures
can be synthesized. For example, by increasing the number of
phenylene units in the linker of the well-known MOF-74 (M2[DOT],
where M2+ = Zn or Mg and DOT = dioxidoterephthalate) from 1 to
2, 3, 4, 5, 6, 7, 9, or 11, Yaghi et al. prepared a series of isoreticular
MOF-74 structures with pore apertures ranging in size from 14 to
98 Å.2 The successful synthesis of MOFs with large pores may
enable the conversion of large molecules in the liquid phase. In
addition, tunability of the pore size enables the design of MOFs
with pore sizes that permit the inclusion of NEs of various sizes.
Moreover, the diffusivity of guest molecules in MOFs, which is of
fundamental importance for their potential applications, can be
systematically studied.
2.1.3 Large pores with small windows. Typical cage-like
MOFs possess abundant interconnected three-dimensional (3D)
cavities that are accessible through small pore windows. For
example, MIL-101,3 which is a representative mesoporous MOF
(meso-MOF), contains two types of large cavities with free
diameters of ca. 2.9 and 3.4 nm. These cavities are accessible
through pore windows with diameters of ca. 1.2 and 1.6 nm,
respectively. This characteristic of MOFs makes them ideal hosts
for accommodating NEs in their large cavities and simultaneously
prevents the internalized guests from leaching or aggregating.
Therefore, isolated and surfactant-free NEs with no restrictions on
their degree of freedom might be obtained. Moreover, the con-
necting window may provide access for the simpler diffusion
of substrates into and out of the cavities to reach active sites
encapsulated in MOFs for efficient catalysis.
2.1.4 Uniform pore structure. Owing to their crystallinity,
MOFs consist of uniform cavities distributed throughout their
4616 | Chem. Soc. Rev., 2017, 46, 4614--4630
View Article Online
Tutorial Review
3D structure with long-range order. Therefore, the use of MOFs
as hosts enables the ordered arrangement of discrete guest
molecules throughout the MOF lattice and thus facilitates the
investigation of interactions between host MOFs and trapped
guests by crystallographic methods (e.g., X-ray crystallography).
2.1.5 Multiple functional sites. MOF materials can be
functionalized by modifying the linkers and metal nodes or
by encapsulating NEs. The integration of multiple functional
sites into a single system can allow them to work cooperatively
and synergetically, which is difficult to achieve in other materials.
For instance, MOFs have found applications in optoelectronics,
with the metal-containing nodes acting as semiconductors
separated by light-sensitive organic struts. Their photocatalytic
performance can be enhanced by encapsulating active NEs
within the pores of MOFs.7
2.1.6 Mild synthesis conditions. There have been successful
efforts to synthesize MOFs (e.g., ZIF-8, MIL-88, HKUST-1, and
Tb-BDC) under room-temperature/ambient conditions. Mild syn-
thesis conditions are important for retaining the activity and
stability of NEs when the bottle-around-ship (Section 3.2) and
in situ encapsulation (Section 3.4) strategies are used for the
fabrication of NE@MOF composites. The development of mild,
operationally simple, low-cost, and scalable reaction conditions
would be likely to pave the way to the development of practical
applications of MOF-based materials.
2.2 Challenges
2.2.1 Poor thermal and chemical stability. The practical
application of MOFs is hindered by their low stability, which
originates from their weak metal–linker coordinate bonds. Most
MOFs undergo extensive decomposition at elevated temperatures.
This journal is © The Royal Society of Chemistry 2017
 View Article Online

Tutorial Review Chem Soc Rev

In addition, exogenous molecules can be inserted into the

metal–linker bonds, which thus disrupts the framework and
decreases the chemical stability of MOFs. The development of
stable MOF materials is crucial if they are to find industrial
applications.
Three main approaches have been considered for enhancing
Published on 18 May 2017. Downloaded by Indian Institute of Technology - Jammu on 7/13/2023 8:55:06 AM.

the stability of MOFs. One involves the preparation of stable

MOFs by direct synthesis using highly acidic metals or highly
basic linkers, which results in the formation of strong metal–
linker bonds. The second comprises functionalizing the organic
linkers to shield the metal–linker bonds from interactions with
exogenous molecules. The third involves coating MOFs with a
protective layer. These approaches can improve the thermal and
chemical stability of pure MOFs to a certain degree. However,
further work on improving the stability of MOF-encapsulated
NEs remains to be carried out.
2.2.2 Limited range of pore sizes. Most MOFs reported to
date fall into the microporous range (pore sizes of o2 nm).
This small pore size hinders the diffusion of chemical species
and limits their interactions with the active sites in MOFs. As
was mentioned above, increasing the length of the organic
linkers and the use of bulky organic scaffolds are useful tools
for the synthesis of meso-MOFs. Nevertheless, the synthesis of
such linkers is complex, and the obtained MOFs almost inevit-
ably present problems with interpenetration, disintegration,
and instability. These difficulties prevent this functionalization
method from being generally adopted for the formation of
meso-MOFs.
Fig. 2 Strategies for fabrication of NE@MOF composites: (a) ship-in-
Recently, templating methods, etching methods, template- bottle, including (a1) post-assembly incorporation of NE precursors and
free methods, and defect-induced methods have been developed (a2) pre-assembly incorporation of NE precursors, (b) bottle-around-ship,
to create hierarchical structures within bulky MOF crystals. (c) sandwich assembly, and (d) in situ encapsulation. Cyan, SBUs of MOFs;
Nevertheless, the control of the sizes, shapes, spatial distribution, gray, organic linkers; orange, precursors or NEs; red, stabilizing agents.
Adapted from ref. 14 with permission from The Royal Society of Chemistry,
and long-range ordering of the pore structure of MOFs remains a
copyright 2014.
great challenge.

introduced into a framework that has already been formed,

3. Methods of encapsulating NEs in
MOFs
The performance of NE@MOF composites is strongly influenced
by the spatial distribution and nanostructure of the incorporated
NEs, as well as by guest–host interactions. The development of
facile methods for the simultaneous control of these parameters
can be expected to enable the design of highly active and stable
NE@MOF functional materials. Four well-established strategies
have been exploited for encapsulating NEs within MOFs, namely,
ship-in-bottle, bottle-around-ship, sandwich assembly, and in situ
encapsulation (Fig. 2).
3.1 Ship-in-bottle strategy (assembly of NEs inside MOFs)
The ship-in-bottle strategy involves the assembly of NEs in an
MOF matrix that has already been formed, which can be accom-
plished by either of two methods, namely, post-assembly incor-
poration and pre-assembly incorporation, depending on how the
NE precursors are incorporated into the matrix (Fig. 2a-1 and a-2).
In the post-assembly incorporation method the NE precursors are
whereas in the pre-assembly incorporation method they are
introduced by being anchored to the linker prior to the assembly
of the MOF. Both these methods rely on the fact that the MOF
pores restrict the growth of the NEs, so that they remain small.
The interface between NEs and MOFs produced by these methods
is relatively chemically simple.
Nevertheless, some problems remain to be solved. (1) The
MOF needs to be stable under the conditions used to form the
NEs. (2) The formation of NEs that are larger than the pore
diameter of the MOF can result in partial degradation of the
framework. (3) The precise control of the internal location,
composition, structure, and shape of the NEs within the frame-
work is challenging. (4) In the post-assembly incorporation
method NEs are inevitably deposited on the external surface
of MOF crystals because of the difference in diffusion resis-
tance between the external and internal MOF surfaces; external
deposition results in NEs with a wide size range, as well as a
random and unpredictable spatial distribution. (5) Although
the pre-assembly incorporation method enables the introduc-
tion of completely isolated and uniform precursors into the

This journal is © The Royal Society of Chemistry 2017 Chem. Soc. Rev., 2017, 46, 4614--4630 | 4617

Chem Soc Rev
MOF pores, the precursors need to be stable during the synthe-
sis of the MOF.
3.2 Bottle-around-ship strategy (assembly of MOFs
around NEs)
The bottle-around-ship strategy involves the assembly of MOF
Published on 18 May 2017. Downloaded by Indian Institute of Technology - Jammu on 7/13/2023 8:55:06 AM.
precursors around NEs that have already been synthesized
(Fig. 2b). Normally, this strategy involves a two-step process:
(1) NE cores with uniform sizes, shapes, and structures are pre-
pared, and (2) MOFs are assembled on the NE surfaces. Capping
agents or surfactants are indispensable for stabilizing the NEs and
facilitating the overgrowth of the MOF on the NEs.
Because the NEs are synthesized before encapsulation, their
nanostructures can be controlled and their particle size is not
limited by the pore size of the MOF. However, in this strategy
achieving the controlled overgrowth of MOFs on NEs rather
than self-nucleation is challenging owing to the high interfacial
energy barrier between the two materials. In addition, the inter-
face between the MOFs and NEs is complex because of the pre-
sence of the NE capping agents, which can alter or degrade the
performance of the NEs.
3.3 Sandwich assembly strategy (embedding NEs between
MOF layers)
The sandwich assembly strategy involves the synthesis of an
MOF core followed by the deposition of NEs and the subsequent
overgrowth of an MOF shell with a tunable thickness on the
MOF core. Moreover, multi-layered materials with controllable
structures can be obtained by repeating the steps of NE deposi-
tion and MOF overgrowth. This strategy enables good control of
the location, composition, and shape of the encapsulated NEs.
The main challenge in this approach is achieving conformal
overgrowth of fracture-free shells on the core. The use of two
MOFs with similar crystal topologies is preferable, because in
that case the crystal lattices of the inner and outer MOFs are
well matched. When two MOFs with mismatched topologies are
used, cationic surfactant capping agents such as cetyltrimethyl-
ammonium bromide are necessary to facilitate the formation of
a conformal fracture-free shell.8
3.4 In situ encapsulation (simultaneous synthesis of
MOF and NEs)
To save time and energy and reduce costs, an operationally
simple in situ encapsulation strategy was recently developed for
preparing NE@MOF composites. This strategy involves mixing
all the necessary constituents (e.g., precursors of the NEs and
MOFs) in solution, whereby the NE and MOF are produced
simultaneously and MOF shells grow exclusively on the surface
of the NE without self-nucleation. Control of the experimental
parameters (e.g., precursors, solvents, surfactants, reaction tem-
perature, and modulators) is necessary to balance the rates of
self-nucleation and growth of the NEs and MOFs and also to
assemble both of them into a single nanostructure. In parti-
cular, the choice of the functional groups in the organic linkers
or solvents is important for stabilizing the NEs formed in situ
and for facilitating the heteronucleation of the MOFs on the
4618 | Chem. Soc. Rev., 2017, 46, 4614--4630
View Article Online
Tutorial Review
surface of the NEs. The one-pot synthesis of NE@MOF compo-
sites may pave the way to practical applications of MOF-based
materials owing to its operational simplicity, low production
cost, and scalability.
However, because the NEs and MOFs form under the same
reaction conditions, synchronous control of the nucleation and
growth of these two distinct components is difficult and, as a
result, the fabrication of complex multiform NE@MOF compo-
sites by means of this strategy is not easy. The development of
novel in situ encapsulation strategies that would enable tuning of
the sizes, shapes, composition, and uniformity of the obtained
hybrid composites is highly desirable.
4. Types of NEs encapsulated in MOFs
4.1 Metal NPs
Metal NPs have recently generated extraordinary interest because
of their high chemical activities and specificities. However, their
high surface energy makes them thermodynamically unstable
and thus prone to aggregate and fuse. The immobilization of
metal NPs in MOFs can prevent the aggregation of NPs and
increase their utility for applications such as heterogeneous
catalysis, gas storage, and chemical sensing. Immobilized metal
NPs can be divided into four basic categories: within-the-pore
structures, which consist of metal NPs in MOF pores; core–shell
structures, which consist of metal cores coated by an MOF shell;
yolk–shell structures, which consist of metal cores inside a
hollow MOF shell; and sandwich structures, which consist of
metal NPs embedded in MOF layers.
4.1.1 Within-the-pore structures. A number of methods
have been developed for the incorporation of NPs into MOFs,
including chemical vapor deposition, solution infiltration, surface
grafting, solid grinding, and microwave irradiation. However,
there are fewer methods for the encapsulation of NPs exclusively
inside the cavities of MOF systems (e.g., the double-solvent
approach and self-redox processes). Work on metal NP@MOF
composites up to 2014 has been the subject of several reviews.1,9–13
Recent research has aimed at developing new methods for precisely
controlling the location, composition, and structure of metal NPs
encapsulated within MOFs.
In contrast to previously reported methods that involved the
introduction of metal precursors into MOFs that had already
been formed, the method proposed by Li et al. involves the
introduction of precursors via anchoring them to the linker prior
to the assembly of the MOF (Fig. 2a-2).14 This method avoids the
problem of the difference in diffusion resistance between the
external and internal surfaces and thus enables the metal precur-
sors to be easily encapsulated in the MOF pores. Li et al. selected a
UiO-67-type MOF, which was based on Zr6O4(OH)4(CO2)12 SBUs
and biphenyldicarboxylic acid (H2bpdc) linkers, as the host matrix
for the encapsulation of Pd NPs owing to its high stability and
the tunability of the linker functionality. The Pd precursor was
immobilized on 2,2 0 -bipyridine-5,5 0 -dicarboxylic acid to form
the metalloligand [(5,5 0 -dicarboxy-2,2 0 -bipyridine)palladium(II)]
dichloride (H2L). To ensure the separation and dispersion
This journal is © The Royal Society of Chemistry 2017

Tutorial Review
of H2L, H2bpdc ligands were employed for the direct synthesis
of Pd-UiO-67 with mixed ligands. By this rational design strategy,
various amounts of Pd were loaded onto UiO-67 by adjusting the
H2L/H2bpdc ratio when the constituents were assembled into
the MOF. As-prepared Pd(II)@UiO-67 was heated at 250 1C under
H2 for 4 h to yield Pd0@UiO-67, which exhibited a uniform
Published on 18 May 2017. Downloaded by Indian Institute of Technology - Jammu on 7/13/2023 8:55:06 AM.
distribution of Pd NPs in a UiO-67 framework with a spherical
diameter of 3.0  0.5 nm.
The ability to tailor the structure of bimetallic NPs encapsu-
lated within the pores of MOFs has been a long-term goal of
scientists, because bimetallic NPs with specific nanostructures
in which both metals are arranged in different patterns might
exhibit interesting and useful structure-dependent properties.
In particular, bimetallic core–shell NPs, in which the inner core
metal can significantly influence the electronic states of the
external shell, which consists of another metal, may exhibit unique
physicochemical properties. However, owing to the inherent micro-
structures of MOFs, controlling the spatial arrangement of metals
in the restricted pores is challenging. Avoiding the separate nuclea-
tion of two metals requires careful control of the reduction and
nucleation processes by means of the choice of an appropriate
reducing agent and reaction system.
Very recently, Li et al. reported a multi-step strategy that
involved seed-mediated growth for the preparation of ultrafine
Pd@Ag core–shell NPs within the pores of an MOF with acti-
vated hydrogen atoms as the reducing agent (Fig. 3).15 Pd NPs
were encapsulated within MOFs that had already been formed.
Then, hydrogen molecules dissociated into activated atomic
hydrogen from the surface of the Pd NPs to serve as effective
reducing agents for the selective deposition of Ag on Pd. The
success of this strategy can be ascribed to the confinement of
Fig. 3 Fabrication of Pd@Ag core–shell NPs encapsulated in MOF pores.
Reprinted from ref. 15 with permission from The Royal Society of Chemistry,
Copyright 2016.
This journal is © The Royal Society of Chemistry 2017
View Article Online
Chem Soc Rev
the activated hydrogen atoms on the surfaces of the encapsu-
lated Pd NPs, which promoted the exclusive reduction of Ag+ on
Pd and prevented the self-nucleated generation of individual
Ag NPs. This method provided ultrafine Pd@Ag core–shell NPs
encapsulated in MOF pores with various Pd/Ag ratios and
average sizes of ca. 2.6–3.1 nm. The Pd@Ag core–shell NPs that
were obtained exhibited a significant enhancement in selectivity
in the partial hydrogenation of phenylacetylene in comparison
with their monometallic counterparts, which was due to the
surface dilution and electronic modification of surface Pd sites
by Ag. The encapsulated miniature Pd@Ag NPs benefited from
the confinement effect exerted by the MOFs and the strong
metal–support interactions and thus displayed high stability
and recyclability in such catalytic processes.
The ability to control the shape of metal nanostructures can
enable the fabrication of materials with unique plasmonic
resonance, catalytic behavior, and sensing ability. For example,
Duan et al. used MOFs with one-dimensional (1D) channels
to synthesize Au and Pt nanowire arrays (Fig. 4).16 MOF-545,
which contains cubic Zr6O8(CO2)8(H2O)8 SBUs and tetrakis(4-
carboxyphenyl)porphyrin linkers, features channel-like pores
with a diameter of B30 Å. The appropriate pH of the gold
chloride solution used during fabrication was essential for
controlling the quality of the nanowire arrays that were formed.
Au@MOF-545 prepared in 0.5 M acetic acid (pH 2.95) exhibited
a high density of ultrathin, well-aligned Au nanowires with
diameters of 2–3 nm.
Great progress has been made in this field, and the develop-
ment of new methods for fabricating faceted nanocrystals with
controlled shapes within MOFs is anticipated and will certainly
enlarge the family of metal@MOFs and lead to a wide range of
advanced applications. In addition, the encapsulation of NPs
that match the cavity size within MOF hosts with a well-defined
spatial order and a homogeneous size dispersion remains a
significant challenge.
4.1.2 Metal NPs coated with an MOF shell. Coating metal
NPs with an MOF shell to form core–shell structures is generally
conducted by means of a two-step procedure. Firstly, surfactant-
capped metal NPs with a well-defined size and morphology are
synthesized, and then the NP surfaces are coated with the MOF.
The shape and structure of the NPs can be well preserved in the
final NP@MOF composites. To date, metal NPs (zero-dimensional),
metal nanowires (1D), metal layers (two-dimensional), and
metal frames (3D) with tunable sizes, compositions, structures,
Fig. 4 Model of MOF-545 with 1D pores as a template for the synthesis of
nanowire arrays. Reprinted from ref. 16 with permission from the American
Chemical Society, copyright 2015.
Chem. Soc. Rev., 2017, 46, 4614--4630 | 4619

Chem Soc Rev
and shapes have been encapsulated within MOF layers.8,17
Moreover, single- and multi-core NP@MOF core–shell structures
can be synthesized by adjusting the incubation temperature and
time at the initial reaction stage.17 In the construction of compo-
sites, effective control of the heterogeneous nucleation of MOFs
onto the metal NP surface to prevent self-nucleation is crucial.
Published on 18 May 2017. Downloaded by Indian Institute of Technology - Jammu on 7/13/2023 8:55:06 AM.
The large lattice mismatch between metal NPs and MOFs results
in enormous interfacial energy between the dissimilar materials,
and this energy has to be counterbalanced to some extent. Ligand
and/or surfactant molecules are consequently required for lattice
compatibility. However, the complete removal of such stabilizing
agents from the final metal NP@MOF nanocomposites is diffi-
cult, and as a result the interfaces between the MOFs and the
metal surfaces tend to be complex and ill defined.
Recently, Li et al. demonstrated that functional groups in
MOF linkers can be employed to stabilize metal NPs and enable
the heterogeneous nucleation of MOFs on metal NPs without
the need for a stabilizing agent.18 Specifically, an N-heterocyclic
carboxylate ligand (e.g., H2bpydc) is used both as a linker of
UiO-67 and as a stabilizer of Pd NPs. During the synthesis of the
composite, H2bpydc (which has a strong affinity for Pd) tends to
adsorb on the surface of Pd NPs as soon as they form, which
thus stabilizes them against aggregation. Subsequently, ZrCl4 is
combined with the adsorbed H2bpydc to form MOFs, which
results in the encapsulation of the Pd NPs in UiO-67. In contrast,
when H2bpdc is employed as the linker, aggregation of Pd NPs is
observed in the final composites. This result implies that the
functional groups on the H2bpydc ligand play an important role
in both stabilizing and encapsulating the Pd NPs.
Because the abovementioned strategy is limited to MOFs with
certain functional groups (such as NH2 and pyridyl), Li et al. also
developed a kinetically modulated one-step protocol that can be
utilised to construct MOFs from traditional aryl carboxylate
linkers (i.e., the largest branch of the MOF family).19 The protocol
involves simple mixing of a reactive metal precursor (e.g.,
H2PtCl6) and an MOF precursor in DMF in the presence of acetic
acid under a mixture of H2 and air (Fig. 5a). DMF plays multiple
roles in the process, acting (1) as a solvent for the formation of
Fig. 5 Incorporation of Pt NPs in a UiO-66 MOF by means of an in situ
one-step protocol (a) with kinetic modulation by H2/acetic acid and (b) with
no modulation. Adapted from ref. 19 with permission from Wiley-VCH Verlag
GmbH & Co., copyright 2016.
4620 | Chem. Soc. Rev., 2017, 46, 4614--4630
View Article Online
Tutorial Review
the MOFs, (2) as a mild reductant for the metal ions, and (3) as a
stabilizer during the formation of Pt NPs. The C–N groups of
DMF may preferentially adsorb on the surface of the Pt NPs that
are generated, whereas the CQO groups may interact with the
hard oxophilic metal cation (Zr4+) of the MOFs, according to
the well-established hard–soft acid–base principle. As a result,
the MOFs preferentially assemble around the Pt NPs that are
formed in situ. H2 increases the rate of Pt ion reduction, and
acetic acid decreases the rate of MOF formation. By means of this
rationally designed protocol, effective control of the size and
spatial distribution of ‘‘clean’’ Pt NPs within UiO-66 could be
achieved, with nanomaterials that exhibit high activity and stabi-
lity in the oxidation of alcohols, as well as molecular sieving
capability (provided by the MOF shell). In the absence of either H2
or acetic acid, the Pt NPs form relatively slowly with respect to the
MOFs, and thus the distribution of the Pt NPs is uneven and
uncontrolled. This results in a remarkable reduction in activity
and poor shape selectivity (Fig. 5b).
No studies involving tuning of the sizes, compositions, and
shapes of metal NPs encapsulated under surfactant-free condi-
tions have yet been published, which suggests that much work
remains to be carried out in this area.
4.1.3 Yolk–shell structures. Yolk–shell structures, which
have a distinctive core@void@shell configuration, have also
generated considerable interest owing to their complex hier-
archical nanostructures. Since the first example was reported
by Tsung et al., hard-template and template-free methods have
been demonstrated to be useful for the design of yolk–shell
MOF structures with single-metal cores.8 However, the shells of
these nanostructures are composed of polycrystalline MOFs, which
can contain defects or cracks. Very recently, much research effort
has been devoted to the development of yolk–shell MOF structures
with single- or multiple-metal cores and single-crystal MOFs.
For example, a sacrificial-template strategy was employed to
synthesize Au@ZIF-8 yolk–shell nanoreactors consisting of a
single-crystal MOF shell with introduced macropores, each of which
contained an Au NP (Fig. 6).20 A typical synthesis involved a multi-
step process comprising (1) the initial growth of core–shell Au@silica
NPs, followed by (2) encapsulation of the NPs in a single-crystal ZIF-8
shell, and (3) etching of silica layers to create the macropores.20 This
Au@ZIF yolk–shell nanoreactor could increase the accessibility of
Au NPs to reactants and also improve the mass transfer kinetics of
reactants and products via its molecular sieving capability.
Yolk–shell metal@single crystal MOF composites have also been
prepared without the use of sacrificial templates. For example,
Fig. 6 Synthesis of an Au@ZIF-8 nanoreactor. Reprinted from ref. 20 with
permission from Wiley-VCH Verlag GmbH & Co., copyright 2016.
This journal is © The Royal Society of Chemistry 2017
 View Article Online

Tutorial Review Chem Soc Rev

Wu et al. recently reported the preparation of a Pd@H-Zn/Co-ZIF

yolk–shell composite by means of a phase transformation from a
sandwich-like structure containing Pd NPs embedded between a
ZIF-67 core and a ZIF-8 shell under solvothermal conditions in
methanol,21 which is a solvent that was discovered to affect the
coordination mode of ZIF-67 in the presence of Co2+. The hollow
Published on 18 May 2017. Downloaded by Indian Institute of Technology - Jammu on 7/13/2023 8:55:06 AM.

structure of Pd@H-Zn/Co-ZIF that was obtained could enhance

gas storage and accelerate product desorption. As a result, the
Pd@H-Zn/Co-ZIF yolk–shell composite with a hollow structure
exhibited enhanced catalytic activity in the oxidation of CO in
comparison with Pd@S-Zn/Co-ZIF core–shell composites with a
solid structure.
Although great success has been achieved in the synthesis of
yolk–shell structures, capping agents such as polyvinylpyrrolidone
are required. The development of effective methods for the
incorporation of ‘‘clean’’ metal NPs within hollow MOFs is a
desirable, albeit challenging, goal.
4.1.4 Sandwich structures. The sandwiching of metal NPs
between two layers of MOFs is an effective strategy for achieving
good contact between the entire surface of the NPs and the
MOF support.22 The first use of this strategy was reported by
Zeng et al.23 As a host material, these investigators chose ZIF-8,
which is a typical member of the ZIF subfamily of MOFs, which
are based on simple zeolite structures. Au NPs stabilized with
3-mercaptopropionic acid were distributed on ZIF-8 nanocrystals
with both rhombic dodecahedron and cubic hexahedron morphol-
ogies. The carboxylate anion and thiol group of the organic acid
mediated the interaction between the incorporated metal NPs and
the ZIF-8 phase. The as-formed ZIF-8@Au hybrid nanocomposites
were then used as cores for the epitaxial growth of an outer layer of
ZIF-8 to form sandwich ZIF-8@Au@ZIF-8 hybrids (Fig. 7).
Fig. 8 Synthesis of MIL-101@Pt@MIL-101 composites comprising Pt NPs
sandwiched between a core and a shell of MIL-101. Reprinted from ref. 22
with permission from Nature Publishing Group, copyright 2016.
Repeating this process gave rise to the formation of multiple
ZIF-8@Au nanostructures, in which additional layers of Au NPs
could be sequentially introduced. The same processes were also
used to embed Ag NPs within ZIF-8 layers.
Tang et al. extended this strategy to carboxylate-based MOFs
(Fig. 8).22 By means of a process of direct homoepitaxial growth,
an MIL-101(Fe)@Pt@MIL-101(Fe) composite with a sandwich
nanostructure could be synthesized. The thickness of the outer
MIL-101(Fe) shell could be steadily increased with an increase
in the concentration of the MOF precursors. The encapsulation of
Pt NPs within MIL-101(Fe)@Pt@MIL-101(Fe) effectively altered the
electron density and thus the catalytic activity of the final materials.
Moreover, these investigators used this method to prepare other
sandwich structures, including MOF-525(Zr)@Pt@MOF-525(Zr),
MOF-74(Co)@Pt@MOF-74(Co), UiO-66(Zr)@Pt@UiO-66(Zr), and
UiO-67(Zr)@Pt@UiO-67(Zr).
In addition to zero-dimensional metal NPs, two-dimensional
metal layers could also be combined with MOFs to form sand-
wich structures. For example, Huo et al. prepared metal layer/
MOF hybrid thin films by alternately growing MOF thin films
and sputter-coating metal layers.24 The number of layers in
Pt/ZIF-8 hybrid thin films could be readily tuned simply by
repeating the growth and coating processes (Fig. 9). This encap-
sulation strategy was extended to other types of metal layers and
MOFs, including Pt/ZIF-67 and Au/ZIF-8 hybrid thin films.
The sandwich structure is ideal for encapsulating NPs with
various shapes, structures, and functionalities. Research in this
field is still in its infancy, and the development of novel strategies
is highly desirable for the fabrication of metal NPs with tunable
structures.

Fig. 7 Transmission electron microscopy images of Au@ZIF-8 hybrid
nanocomposites with various geometric combinations: (a) RD@Au@RD,
(b) RD@Au@NC, (c) NC@Au@RD, and (d) NC@Au@NC (RD = rhombic
dodecahedron and NC = cubic hexahedron). Reprinted from ref. 23 with
permission from the American Chemical Society, copyright 2013.
4.2 QDs
QDs (with a size range of 2–10 nm) have received considerable
attention over the last two decades owing to their uniquely size-
dependent electronic and optical properties. The encapsulation
of QDs within MOFs can enhance their stability and modulate
electron–hole recombination rates. Several types of QDs (e.g.,
oxide-, chalcogenide-, nitride-, and carbon-based QDs) have

This journal is © The Royal Society of Chemistry 2017 Chem. Soc. Rev., 2017, 46, 4614--4630 | 4621
 View Article Online

Chem Soc Rev Tutorial Review

composite consisting of CdSe–CdS–ZnS core–shell QDs in

MOF-5 was designed.
However, the use of capping agents can passivate QDs,
which thus decreases their fluorescence. To circumvent this
problem, Banerjee et al. developed a capping agent-free strategy
for encapsulating CdS within MOFs.29 Uncapped CdS QDs are
Published on 18 May 2017. Downloaded by Indian Institute of Technology - Jammu on 7/13/2023 8:55:06 AM.

first trapped in a low-molecular-weight metallohydrogel (ZAVA),

which is transformed into a xerogel form (CdS@ZAVA xerogel)
and is then converted into a CdS-loaded MOF (CdS@ZAVCl)
via a unique process mediated by sodium chloride (Fig. 10).
This synthesis-cum-entrapment procedure does not require a
capping agent and therefore the QDs are well exposed after
encapsulation.
Fig. 9 (a)–(e) Transmission electron micrographs of Pt/ZIF-8 hybrid thin films
In order to achieve better control of the shape of the final
comprising one to five layers, respectively, and (f) X-ray diffraction patterns of composites, Kong et al. developed a self-templating strategy
the five films. Reprinted from ref. 24 with permission from Tsinghua University for the synthesis of ZnO@ZIF-8 nanorod arrays (Fig. 11).30
Press and Springer-Verlag Berlin Heidelberg, copyright 2015. Specifically, ZnO nanorods act as sacrificial templates to provide
metal ions and then initiate the growth of MOFs. In this way, the
morphology of the initial ZnO nanorods is preserved in the final
been integrated into MOFs, and the resulting composite materials composite. A detailed investigation of the reaction conditions
exhibit properties that make them useful in a wide range of suggested that the solvent composition and reaction temperature
fields such as photocatalysis, supercapacitors, and sensing.25
The following are the three most common types of QD@MOF
composites: within-the-pore structures, core–shell structures,
and sandwich structures.
4.2.1 Within-the-pore structures. The fabrication of QDs
inside MOF pores typically involves the solution or vapor infiltra-
tion of QD precursors into MOFs, followed by the transformation
of the precursors into the corresponding QDs.26
As an alternative to the infiltration of external QD precursors
into MOF pores, MOFs can themselves serve as sources of metal
precursors upon partial thermal decomposition. For example,
a sacrificial-template method for the fabrication of CuS QDs in
and on Cu3(BTC)2(H2O)3 (BTC = 1,3,5-benzenetricarboxylate)
was recently disclosed.27 A series of composites were prepared
by immersing Cu3(BTC)2(H2O)3 in a solution in EtOH of thio-
acetamide as a sulfide source. The CuS loading in the composite Fig. 10 (top) Production of CdS-loaded ZAVCl MOF (CdS@ZAVCl-MOF)
from CdS-loaded ZAVA gel (CdS@ZAVA gel) and space-filling representation
was controlled by varying the reaction time and temperature.
of the crystal structure of ZAVCl (viewed along the c-axis). Gray, carbon;
The electrical conductivity of the composites increased with an white, hydrogen; purple, zinc; green, chlorine; blue, nitrogen; red, oxygen.
increase in the amount of CuS in the composite at the expense (bottom) Real-time digital photographs of the process of the conversion of
of the porosity. Regardless, the composites exhibited superior the CdS@ZAVA gel into the CdS@ZAVCl MOF. Reprinted from ref. 29 with
electrocatalytic activity in the ORR with respect to the parent permission from the American Chemical Society, copyright 2014.
Cu-BTC or CuS.
4.2.2 Core–shell structures. MOFs can be assembled on pre-
formed QD surfaces. This process generally requires a capping
agent or surfactant to stabilize and disperse the QDs in the MOF
growth medium and to encourage heteronucleation of the MOF
on the QD surfaces.28 The capping agent usually acts as a bridge
to ensure good contact between the MOF and QDs. Recently,
an elegant strategy was disclosed for functionalizing MOFs with
QDs using a surfactant as a carrier.28 The strategy relies on the
discovery that ceramic desert rose microparticles (DRMs, a-hopeite
microparticles) formed from a surfactant coordinated with Zn2+
have an exceptional ability to act as seeds for the nucleation of Fig. 11 Synthesis of ZnO@ZIF-8 nanorod arrays via a self-templating strategy.
MOFs. Therefore, QDs supported on DRMs can be introduced Reprinted from ref. 30 with permission from the American Chemical Society,
into MOFs. Using DRMs doped with QDs, a QD/DRM/MOF-5 copyright 2013.

4622 | Chem. Soc. Rev., 2017, 46, 4614--4630 This journal is © The Royal Society of Chemistry 2017

Tutorial Review
are crucial for effective control of the quality of the final com-
posites. Owing to the molecular sieving capability provided
by the ZIF-8 shells, the ZnO@ZIF-8 nanorod arrays displayed
different photoelectrochemical responses to hole scavengers
with various sizes.
4.2.3 Sandwich structures. QDs can be controllably incor-
Published on 18 May 2017. Downloaded by Indian Institute of Technology - Jammu on 7/13/2023 8:55:06 AM.
porated into MOF films to form a sandwich structure by the
repetition of a cycle that consists of the growth of an MOF thin
film followed by spin-coating with QDs. For example, CdSe/ZIF-8
has been prepared by spin-coating polyvinylpyrrolidone-capped
CdSe QDs onto a thin film of ZIF-8, followed by the further
growth of MOFs. Repeating these steps resulted in the construc-
tion of multi-layered composites.31
4.3 POMs
POMs are a family of nano-sized metal oxide polyanions with
rich structural and chemical variety and tunable shapes, sizes,
solubilities, redox potentials, and acidities. However, their appli-
cations are limited by their small specific surface area, low
stability, and high solubility in aqueous solution. The incorpora-
tion of POMs into MOFs is a promising approach for stabilizing
and optimizing POMs to improve their utility. There are several
well-established effective methods for preparing POM@MOF
composites: impregnation of POM clusters into MOF pores,
synthesis of POMs inside the cages of MOFs that have already
been formed, and synthesis of MOFs in the presence of POMs.32,33
Although the impregnation method is straightforward, it is
limited to MOFs with window openings that are larger than the
respective POMs. Moreover, some POM molecules are inevitably
deposited on the external surface of MOFs and are thus subject to
leaching. The synthesis of POMs inside MOFs that have already
been formed has also previously been attempted.32 However, the
synthesis of POMs generally requires strongly acidic conditions,
which result in the degradation of MOFs. The assembly of MOFs
on POMs, which has recently received a lot of attention, has
proved to be useful for the construction of hybrid composites.
Their efficient assembly is expected to depend on control over
reaction parameters such as the concentration and type of
metal oxide anions and heteroatoms, pH, ligands, and reaction
temperature.
Roch-Marchal et al. investigated the methods described
above for the encapsulation of a representative POM, namely,
phosphomolybdate [PMo12O40]3 Keggin heteropolyanion, into
FeIII
3 O(H2O)2(F){C6H3(CO2)3}2nH2O (n = 14.5), also known as
MIL-100(Fe).34 These investigators found that the impregnation
of MIL-100(Fe) with an aqueous solution of H3PMo12O40 enabled
the adsorption of the POM only on the external surface of MIL-
100(Fe) because of the small window size of the MOF. Moreover,
MIL-100(Fe) underwent partial degradation in the acidic solution
of the POM (pH 1.8). An attempt to synthesize [PMo12O40]3 in
the presence of MIL-100(Fe) also failed because of the strongly
acidic conditions that were required (pH 1.8). However, the
assembly of MIL-100(Fe) around the POM was demonstrated to
be an effective strategy, and careful control of the reaction para-
meters was key for the success of this method. Roch-Marchal
et al. chose iron chlorides instead of iron metal to avoid reduction
This journal is © The Royal Society of Chemistry 2017
View Article Online
Chem Soc Rev
Fig. 12 Preparation of [Cu3(BTC)2]n nanocrystals modulated by POM and
water (middle panel). Representative transmission and scanning electron
micrographs of various uniform [Cu3(BTC)2]n crystals prepared by Wang
et al. are shown in the top and bottom panels (scale bars = 200 nm).
Reprinted from ref. 35 with permission from Science China Press and
Springer-Verlag Berlin Heidelberg, copyright 2015.
of the phosphomolybdate ion during the synthesis. The organic
linker BTC was esterified in advance to enable better control of
the reaction kinetics, which resulted in a more crystalline MIL-
100(Fe) solid. The synthesis was typically conducted by mixing
H3PMo12O40, FeCl36H2O, and trimethyl BTC in water at 130 1C
for 3 days to afford H3PMo12O40@MIL-100(Fe). The encapsulated
H3PMo12O40 benefited from the protection afforded by MIL-101(Fe)
against leaching and exhibited remarkable stability after 2 months
in aqueous solution.
The use of POMs as templates may alter the equilibrium
between the metal ions and organic linkers and thus may enable
the manipulation of the nucleation and growth of MOFs to achieve
shape-controlled synthesis of MOF nanocrystals. Wang et al. used
a Keggin-type POM (sodium phosphotungstate) as a coordina-
tion modulator to facilitate the synthesis of [Cu3(BTC)2]n.35 By
increasing the amount of POM, they obtained MOFs with con-
trolled morphologies that varied from hollow cages to solid
octahedral nanocrystals with different degrees of truncation
(Fig. 12). These investigators demonstrated that the POM anions
interacted with the Cu(II) cations, which thus reduced the
concentration of free metal cations and enabled effective control
of the release of Cu(II). This, in turn, enabled separation of the
nucleation and growth processes so that [Cu3(BTC)2]n grew to
form uniform nanocrystals.
4.4 Organic and metallorganic molecules
Homogeneous organic and metallorganic molecules (e.g.,
porphyrins and their metal derivatives, salen complexes, metal
phthalocyanine complexes, and dyes) have been extensively
investigated as tools for understanding and mimicking the
functionalities of biological systems. However, the activity lifetimes
Chem. Soc. Rev., 2017, 46, 4614--4630 | 4623
 View Article Online

Chem Soc Rev Tutorial Review

of these molecules are limited owing to self-aggregation as a

result of reactions between the active sites and oxidative self-
degradation. The immobilization of these molecules in MOFs,
where the active sites can be isolated and protected, is a pro-
mising approach for overcoming this drawback. Metallorganic
complexes can be introduced into MOFs by incorporation in
Published on 18 May 2017. Downloaded by Indian Institute of Technology - Jammu on 7/13/2023 8:55:06 AM.

organic linkers or encapsulation in MOF pores. Here, we focus

on the latter approach.
Metallorganic complex@MOF composites can be simply
prepared by wet infiltration as long as the pore windows of
the MOFs are larger than the molecular size of the complex.
Farrusseng et al. systematically investigated the wet infiltration
method to encapsulate metal phthalocyanine complexes of dif-
ferent sizes in MIL-101.36 Wet infiltration of solutions of FePcF16
and RuPcF16 into MIL-101 at a maximum theoretical loading of
9 wt% gave actual loadings of 2.1 and 3.6 wt%, respectively. The
total pore volume percentage of FePcF16@MIL-101 was 16% (i.e.,
less than that of the parent MIL-101), and the difference in pore
volume was greater than was expected on the basis of a loading Fig. 13 Incorporation of relatively large, diverse guest molecules into MOFs
of 3.6 wt%. This difference clearly demonstrated that FePcF16 under linker exchange conditions. Reprinted from ref. 37 with permission
was incorporated into the porous MOF structure. However, the from the American Chemical Society, copyright 2014.
(FePctBu4)2N complex (2.0  2.0 nm) was too large to enter
the hexagonal pore windows of MIL-101 (1.47  1.6 nm) and
already been formed, an MOF can serve as a nanoreactor for
thus was found mostly on the external surface of the MOF, as
the assembly of functional species within its pores, and the latter
evidenced by the fact that the total pore volume of the compo-
strategy can be used to incorporate molecules that are larger than
site was only 5% less than that of the pure MOF; this decrease
the MOF windows. For example, Ma et al. proposed a de novo
in pore volume corresponds to a weight gain of 5.2 wt% after
assembly approach directed by metal cations38 that involved two
loading. The benefit of encapsulating homogeneous catalysts
steps: (1) the exchange of exogenous metal ions with cations in
in MOF pores was demonstrated in the selective oxidation of
an MOF containing metal cations and (2) the assembly of guest
tetralin to 1-tetralone. FePcF16@MIL-101 exhibited a turnover
molecules in the MOF pores.
number that was almost eight times higher in comparison with
To illustrate this strategy, these investigators used Zn8(ad)4-
that of the homogeneous FePcF16 catalyst, which could be
(bpdc)6O2Me2NH2 (ad = adeninate; bio-MOF-1), which is an
attributed to synergistic effects arising from confinement in
MOF that contains Me2NH2+ cations residing in 1D channels.
the MOF pores. In contrast, (FePctBu4)2N@MIL-101 exhibited a
When bio-MOF-1 was immersed in a solution in methanol of
turnover number that was similar to that of (FePctBu4)2N, which
Co(Ac)2, Me2NH2+ ions exchanged with Co(II) ions and the resulting
was consistent with the hypothesis that (FePctBu4)2N was deposited
Co@bio-MOF-1 was then placed in a solution in formamide of
on the external surface of MIL-101.
1,2-dicyanobenzene at 190 1C for the assembly of Co(II) phthalo-
To address the limitations of the diffusion strategy, which is
cyanine (CoPc) in bio-MOF-1 (Fig. 14). This strategy was applicable to
only capable of introducing guests that are smaller than the
other metal phthalocyanine compounds, such as NiPc@bio-MOF-1
MOF window size, Tsung et al. developed a process of disso-
and CuPc@bio-MOF-1.
ciative linker exchange for the encapsulation of large guests
A similar concept was applied by Gascon et al. to encapsulate
(i.e., those with molecular diameters of 3–4 times the size of the
a molecular Co catalyst within an MOF using a ‘ship-in-bottle’
framework apertures).37 This strategy takes advantage of the
strategy.7 This strategy involved a two-stage process, i.e., the
phenomenon of dissociative linker substitution, which is observed
encapsulation of the organic component C11H20N4O2 in the pores
in MOFs under specific conditions. This phenomenon results in
of NH2-MIL-125(Ti), followed by the addition of CoBr2 to assemble
short-lived linker vacancies that can momentarily expand the pore
apertures and thus enable the inclusion of large guests into the
pores (Fig. 13). Tsung et al. used ZIF-8, which has aperture and
pore sizes of B3.4 and 11.6 Å, respectively, and rhodamine 6G,
which has a molecular diameter of 11.3–13.7 Å, as a model host
and guest, respectively, for proof-of-concept experiments. Typically,
rhodamine 6G was incubated with ZIF-8 in the presence of
2-methylimidazole as an exogenous linker in butanol at 100 1C
for 7 days. The guest loading was temperature- and solvent- Fig. 14 De novo assembly of CoPc@bio-MOF-1. (a) Me2NH2+@bio-MOF-1,
dependent. This strategy was also used to encapsulate PPh3 in (b) Co@bio-MOF-1 and (c) CoPc@bio-MOF-1. Reprinted from ref. 38 with
ZIF-8. In addition to acting as a host for guests that have permission from the American Chemical Society, copyright 2014.

4624 | Chem. Soc. Rev., 2017, 46, 4614--4630 This journal is © The Royal Society of Chemistry 2017

Tutorial Review
Published on 18 May 2017. Downloaded by Indian Institute of Technology - Jammu on 7/13/2023 8:55:06 AM.
Fig. 15 ‘Ship-in-bottle’ synthetic strategy developed for the assembly of
Co@MOF. Reprinted from ref. 7 with permission from The Royal Society of
Chemistry, Copyright 2015.
the complex 1. Because the dimensions of complex 1 are larger
than the size of the MOF windows, the Co compound could be
confined within the MOF pores (Fig. 15). The combination of
a photoactive MOF and a Co-based proton reduction catalyst
derived from 1 was proved to be highly successful for applications
in H2 evolution and led to a 20-fold enhancement in performance
in comparison with that of pristine NH2-MIL-125(Ti).
Functional molecules can also be used as templates for the
synthesis of MOFs. Eddaoudi et al. adopted the bottle-around-ship
strategy to encapsulate a porphyrin, namely, 5,10,15,20-tetrakis-
(1-methyl-4-pyridinio)porphyrin tetra(p-toluenesulfonate), also
known as H2TMPyP(p-tosyl)4, in an indium imidazoledicarboxylate-
based rho-ZMOF.39 The rho-ZMOF was chosen because of its
large cavities with relatively small openings, mild synthesis
conditions, and high stability in aqueous media. The reaction
of the MOF precursors in a mixture of DMF/acetonitrile in the
presence of H2TMPyP(p-tosyl)4 yielded the final composites.
Electrostatic interactions between the cationic porphyrin and
the anionic framework played an important role during the
encapsulation processes. The encapsulated porphyrin free base
could be further metallated by exposing (H2TMPyP)4+@ZMOF
to various solutions of transition metal ions. As-synthesized
MnTMPyP@ZMOF composites gave rise to a noticeably higher
yield in comparison with metalloporphyrins supported on other
systems (e.g., zeolites or mesoporous silicates) in the oxidation
of cyclohexane.
Furthermore, Zaworotko et al. found that metalloporphyrins
can template the synthesis of MOFs that cannot be prepared
in the absence of porphyrins.40 Specifically, mixing M(II)Cl2
(M = Fe, Co, Mn, Ni, Mg, or Zn) with BTC in the presence of
meso-tetra(N-methyl-4-pyridyl)porphine tetratosylate in DMF
This journal is © The Royal Society of Chemistry 2017
View Article Online
Chem Soc Rev
and H2O yielded six porph@MOFs composites. Pure MOFs
could not be prepared in the absence of the porphyrin. The
crystal structures of the composites revealed that the metallo-
porphyrins were selectively encapsulated in the octahemiocta-
hedral cages of the MOFs.
4.5 Biomacromolecules
The utilization of functional biomacromolecules (e.g., proteins,
DNA, and enzymes) in pharmaceuticals and for chemical syn-
thesis has long been a goal of scientists. If active biomacro-
molecules are to find industrial applications, their thermal
stability, tolerance of organic solvents, recyclability, and shelf
life must be enhanced without compromising their activity. MOFs
have been proved to be promising platforms for the immobiliza-
tion of biomacromolecules to shield them from deactivating
reaction conditions (e.g., elevated temperatures, organic solvents,
and denaturants) and improve their recyclability. In this regard,
Farha et al. have recently reviewed enzyme systems encapsulated
in MOFs for the design of robust and active catalysts to be
employed under challenging catalytic conditions.41 Several
strategies have been reported for the immobilization of bio-
macromolecules in MOFs, including physical adsorption, covalent
attachment, dye-tagging, and encapsulation.42 Here, we focus our
discussion on the encapsulation of biomacromolecules in the
pores of MOFs.
The encapsulation of large biomacromolecules in MOF pores
requires that the selected MOF has sufficiently large pores. Using
linker extensions, Yaghi et al. systematically prepared a series
of isoreticular channel-type MOF-74 structures (designated as
IRMOF-74-I-XI) with pore apertures ranging from 14 to 98 Å.2
Among this series, IRMOF-74-VII and IRMOF-74-IX had pores
that were large enough to host natural proteins. Myoglobin
(which is a globular protein with spherical dimensions of 21 
35  44 Å) and green fluorescent protein (which has a barrel
structure with a diameter of 34 Å and a length of 45 Å) were
selected as guests for IRMOF-74-VII and IRMOF-74-IX, respec-
tively. Considering the hydrophilic surfaces of these proteins,
Yaghi et al. functionalized the pores of IRMOF-74-VII and
IRMOF-74-IX with hydrophilic groups (triethylene glycol mono-
methyl ether) to improve protein uptake. In a control experi-
ment on MOFs with pores functionalized with hydrophobic
hexyl chains, it was shown that negligible amounts of protein
were taken up. This work demonstrates that a suitable pore size
and environment are important for the successful incorpora-
tion of proteins into MOFs.
Although biomacromolecules were successfully incorporated
into the abovementioned channel-type MOF materials, the acces-
sibility and conformation of the encapsulated biomacromole-
cules must also be considered in the design of an optimal MOF
bioreactor. MOF hosts with only one kind of 1D channel, such as
MOF-74, provide no pathways for the rapid diffusion of reactants
or products after the immobilization of biomacromolecules
in the pores. To address this limitation, Farha et al. employed
NU-1000, which is a zirconium-based MOF that has a hierarchical
pore structure that can both stabilize an enzyme (e.g., cutinase) and
enable the diffusion of reactants and products.43 The hexagonal
Chem. Soc. Rev., 2017, 46, 4614--4630 | 4625

Chem Soc Rev
Published on 18 May 2017. Downloaded by Indian Institute of Technology - Jammu on 7/13/2023 8:55:06 AM.
Fig. 16 Accessibility of active sites of cutinases immobilized in MOFs.
(A) Perspective views of 1D channels of PCN-600, CYCU-3, and NU-1000.
The purple cylinders represent the channels, and the yellow tunnels indicate
the connectivity between neighboring channels. (B) Enzyme-loading and
surface treatment processes. (C) Maximum loading capacity (black), enzymes
encapsulated in channels (red), and accessible enzymes (blue) in nano-
sized MOFs. Reprinted from ref. 43 with permission from Elsevier, Inc.,
copyright 2016.
channels of NU-1000 have a diameter of 3.1 nm, which matches
the molecular size of cutinase. The triangular channels of the
MOF, which have an edge length of 1.5 nm, do not provide
enough space for the encapsulation of the enzyme but enable
reactants to freely diffuse into and out of the framework. The
superiority of NU-1000 as a support was demonstrated by com-
parison with two other channel-type MOFs (CYCU-3 and PCN-600),
which have similar pore sizes but different metal nodes, organic
linkers, and connectivity (Fig. 16). PCN-600 contains only meso-
pores, which are expected to be blocked by encapsulated cutinase
and thus leave little room for the diffusion of reactants. A titration
experiment revealed that only 6% of the total amount of cutinase
encapsulated in PCN-600 was active. CYCU-3, which has a hier-
archical micro/mesopore structure similar to that of NU-1000 but
condensed walls that prevent the diffusion of reactants between
neighboring channels, was also unsuitable for the immobilization
of cutinase. Moreover, the size of the mesoporous channels in
MOFs should match that of the biomacromolecules when
4626 | Chem. Soc. Rev., 2017, 46, 4614--4630
View Article Online
Tutorial Review
channel-type MOFs with a hierarchical pore structure are
employed for the encapsulation of biomacromolecules. For
example, Farha et al. chose PCN-128y, which is a zirconium MOF
with mesoporous channels (4.4 nm) that are large enough to
confine an enzyme used for detoxifying nerve agents (e.g., organo-
phosphorus acid anhydrolase (OPAA), which has a small-axis
length of B4.4 nm).44 The size-matching encapsulation process
was performed under mild conditions and was capable of encap-
sulating OPAA at high loadings. The as-synthesized composite
exhibited high catalytic performance in detoxifying the nerve
agent stimulant diisopropyl fluorophosphate and the real nerve
agent O-pinacolyl methyl fluorophosphonate with comparatively
higher thermal stability than that of the free enzyme, as well as
superior long-term storage stability.
3D cage-like meso-MOFs may be better platforms in com-
parison with 1D channel-type MOFs for the encapsulation of
biomacromolecules. In principle, they can separate guest mole-
cules into each cage and provide sufficient host–guest interactions.
For the encapsulation of biomacromolecules, MOFs with enzyme-
compatible cages, convenient window sizes, and high stability are
required. Zhou et al. reported that PCN-333(Al) is an ideal platform
for the encapsulation of single enzymes.45 PCN-333(Al) has large
cages (5.5 nm) and is highly stable in aqueous solution. As guests,
these investigators selected three enzymes (horseradish peroxi-
dase, cytochrome c, and microperoxidase-11), all of which have
molecular sizes that are smaller than the channels in PCN-333(Al).
The molecular sizes of horseradish peroxidase and cytochrome c
relative to the size of the MOF cages made them most likely to
undergo single-enzyme immobilization, whereas MP-11 was
expected to undergo multiple-enzyme encapsulation owing to
the mismatch in size. All three enzymes were successfully inter-
nalized into PCN-333(Al) at record high loadings.
However, because the apertures of most common MOFs
are smaller than the molecular sizes of biomacromolecules, a
general method for the preparation of MOFs with encapsulated
biomacromolecules remains a challenge. Falcaro et al. adopted
natural biomineralization processes as a model for the encap-
sulation of biomacromolecules such as proteins, DNA, and
enzymes in MOF shells (Fig. 17).46 These investigators hypo-
thesized that if biomacromolecules and MOF building blocks that
had an affinity for each other were chosen, this would increase the
local concentration of both metal cations and organic linkers,
which would in turn facilitate the nucleation of clusters of MOFs
around the biomacromolecules. Falcaro et al. demonstrated that a
series of biomacromolecules, including ovalbumin, ribonuclease
A, human serum albumin, pyrroloquinoline quinone-dependent
glucose dehydrogenase, lipase, hemoglobin, lysozyme, insulin,
horseradish peroxidase, trypsin, urease, and oligonucleotides,
could be encapsulated within ZIF-8. Moreover, this biomimetic
mineralization approach could be extended to other types of
MOFs, including Cu3(BTC)2 (HKUST-1), Eu2(1,4-BDC)3(H2O)4,
Tb2(1,4-BDC)3(H2O)4, and MIL-88A (an Fe(III) dicarboxylate MOF).
Biomacromolecules encapsulated in ZIF-8 were shown to main-
tain their activity even after exposure to extreme conditions (e.g.,
elevated temperatures and organic solvents) that would otherwise
decompose the pure biomacromolecules.
This journal is © The Royal Society of Chemistry 2017

Tutorial Review
Published on 18 May 2017. Downloaded by Indian Institute of Technology - Jammu on 7/13/2023 8:55:06 AM.
Fig. 17 Biomimetically mineralized MOF. (a) Sea urchins have a hard,
porous protective shell that is biomineralized by soft biological tissue.
(b) MOF biocomposite with a biomacromolecule (e.g., protein, enzyme, or
DNA) encapsulated within a porous crystalline shell. Reprinted from ref. 46
with permission from Nature Publishing Group, copyright 2015.
4.6 Metal–organic polyhedra
Metal–organic polyhedra (MOPs) are a new class of discrete
inorganic–organic coordination complexes synthesized via the
coordination of metal ions and functionalized linkers. Owing to
their tunable structures and high symmetry, MOPs have attracted
considerable attention for employment in applications including
adsorption, catalysis, and molecular sensing. However, the tendency
of MOPs to aggregate after activation compromises their perfor-
mance. Li et al. recently demonstrated that the encapsulation of
MOPs in MOF cavities can isolate individual MOPs, which thereby
enhances their reactivity and stability (Fig. 18).47 MIL-101(Cr) was
selected as the host for these studies, and M6L4 (M = (en)Pd(NO3)2,
en = ethylenediamine, and L = 1,3,5-tris(4-pyridyl)-2,4,6-triazine) was
the model MOP guest. A novel hydrophilicity-directed approach was
Fig. 18 Preparation of (a) M6L4 and (b) M6L4CMIL-101. Reprinted from ref. 47
with permission from the American Chemical Society, copyright 2016.
This journal is © The Royal Society of Chemistry 2017
View Article Online
Chem Soc Rev
attempted. MIL-101(Cr) and L were first added to a hydrophobic
solvent (n-hexane), and then a small amount of an aqueous solution
containing the precursors of M was added (the volume of the
aqueous solution was lower than the pore volume of the MOF).
The aqueous solution of the precursors of M was readily introduced
into the MOF pores by capillary force, because the hydrophilicity of
the inner surface of MIL-101 was higher with respect to that of the
external surface. In addition, M6L4 easily self-assembles in water,
which pushed L into the MIL-101 pores owing to a shift in the
chemical equilibrium. In this way, M6L4 molecules that were
larger in size than the MOF cavities could be embedded within
the MIL-101 pores.
4.7 Other NEs
Other NEs, including polymers, ionic liquids (ILs), silicas, and
carbon nanostructures, have also been employed to form compo-
sites with MOFs and generate new multifunctional hybrid materials.
Polymers are easy to produce and light in weight and exhibit
high thermal and chemical stability. However, functional poly-
mers are often associated with highly ordered crystallinity, which
makes packing and chain alignment difficult to achieve. The
pioneering work of Kitagawa et al. demonstrated that MOFs with
nanochannels of various sizes, shapes, dimensions, and surface
functionalities can serve as nanoreactors for confined polymeri-
zation,48 and this method has been used to control the molecular
weight, tacticity, dimensions, and copolymer sequence of the
resulting polymers. Alternatively, polymers can be used as tem-
plates for the coating of MOFs to form core–shell structures.5
ILs are additional candidates for encapsulation in MOFs.
Although ILs have promising properties such as a negligible
vapor pressure, non-flammability, high thermal and chemical
stability, and high ionic conductivity, their applications are
limited by various drawbacks including high cost, unsuitable
viscosity, tendency to absorb water, and strong interactions with
other ions. The properties of ILs can be tuned or enhanced by
nano-sizing them or incorporating them into host materials
such as MOFs. There are two main strategies that can be effective
for the incorporation of ILs into MOFs, namely, the construction
of ILs inside the pores of MOFs and the ionothermal synthesis of
MOFs in ILs as solvents. Kitagawa et al. have recently reviewed IL
systems supported by MOFs.49
In addition, silicas and carbon nanostructures (e.g., graphites,
fullerenes, nanotubes, and nanodiamonds) can be dispersed within
MOF pores or surrounded by MOF layers. Advances in the nano-
chemistry of silica and carbon in combination with emerging
MOFs can be expected to lead to novel applications.
5. Enhancements in performance of
NEs due to encapsulation in MOFs
The properties of NEs encapsulated in these materials differ from
those of free NEs owing to the nanoconfinement and electron-
regulating effects of MOFs. In this section, we summarize some
of the remarkable enhancements in performance observed for
NE@MOF composites.
Chem. Soc. Rev., 2017, 46, 4614--4630 | 4627

Chem Soc Rev
5.1 Enhanced stability
NEs possess high surface energies and are consequently thermo-
dynamically unstable, with a tendency to aggregate under harsh
conditions, e.g., high temperatures. The encapsulation of NEs
within MOFs is an effective strategy for the enhancement of
their stability. The geometric structures of MOFs can minimize
Published on 18 May 2017. Downloaded by Indian Institute of Technology - Jammu on 7/13/2023 8:55:06 AM.
leaching and aggregation of encapsulated NEs. 3D MOFs with
large cavities interconnected by small windows are particularly
appropriate for the stabilization of NEs. For example, MIL-101(Cr),
which contains two types of mesopore (ca. 29 and 34 Å) and small
pore entrances (12 and 16 Å), has been used to encapsulate M6L4,
which is a typical MOP (molecular size of ca. 2.5 nm).47 The large
cavities of MIL-101 enable the inclusion of M6L4, but the small
pore windows prevent M6L4 from leaching and aggregating. M6L4
encapsulated in MIL-101(Cr) retains its catalytic activity for the
oxidation of benzyl alcohol even after five cycles of use, whereas
non-encapsulated M6L4 was deactivated under the investigated
reaction conditions.
Interactions between MOF hosts and encapsulated guests
can improve the stability of guests in other ways, as illustrated
by Zhou et al., who used PCN-333 to immobilize enzymes.45 The
cages of PCN-333 are surrounded by metal sites with polarized
coordinating water molecules and conjugated organic linkers,
and these species interacted strongly with the hydrophilic and
hydrophobic parts, respectively, of the immobilized enzyme.
These interactions explained the negligible leaching and well-
preserved activity of the enzyme that were observed, even under
harsh conditions. In contrast, the free enzyme suffered from an
irreversible loss of bioactivity owing to the disruption of non-
covalent interactions by variations in temperature or pH.
5.2 Novel activities
Cage-like MOFs can also be used to separate functional NEs
into individual pores, which allows the NEs to be exposed to
reactants and prevents dimerization of the NEs, which results
in a loss of activity. Dimerization and a consequent loss of
activity are commonly observed in homogeneous catalysis using
metal complexes. Ma et al. encapsulated Co(II) phthalocyanine
(CoPc) molecules into bio-MOF-1 and found that the resulting
composite gave a conversion of 72% after reaction for 16 h at
60 1C (using 8 wt% CoPc relative to the mass of styrene) when
used for the epoxidation of styrene, whereas homogeneous
CoPc exhibited a much lower conversion (38%) under identical
reaction conditions.38 The inferior activity of the homogeneous
catalyst may have been due to the formation of CoPc oligomers
in solution by means of p–p stacking.
The metal nodes and aromatic linkers of MOFs can interact
with guests by means of charge transfer via coordination or p–p
forces, and these interactions can regulate the electronic prop-
erties of the encapsulated guests and thus alter their activity.
For example, after the encapsulation of Pd NPs in the pores of
UiO-67, the electron-rich carboxylate moiety of the SBU and
the benzene rings of UiO-67 establish electron-donating inter-
actions with the Pd NPs.14 The resulting formation of anionic
Pd clusters is favorable for the activation of O2, and the
4628 | Chem. Soc. Rev., 2017, 46, 4614--4630
View Article Online
Tutorial Review
composite material exhibits superior efficiency in the oxidation
of alcohols without the need for the addition of a base. In
contrast, Pd NPs deposited on the external surface of MOFs
display weak metal–support electronic interactions and thus
exhibit low catalytic activity.
MOFs can also be used to promote reactions involving gases.
For example, local concentrations of gas molecules around the
active sites in porous MOFs tend to be relatively high, which
results in an increase in activity. For instance, Pd nanocubes
encapsulated in ZIF-8 display superior performance in the
hydrogenation of 1-hexene relative to that of free nanocubes.50
The enhanced activity was attributed to the ability of ZIF-8 to
enrich H2 (as indicated by studies of H2 sorption), and ZIF-8 thus
served not only as a nanoreactor but also as a hydrogen gas
reservoir.
5.3 Molecular sieving effects
NE@MOF composites can also act as molecular sieves owing to
their well-defined porous structures, with remarkable applica-
tions in selective catalysis and sensing. For example, Falcaro et al.
observed that QD/DRM/MOF-5 composites exhibited significantly
different luminescence-quenching behaviors when exposed to
solutions of thiols with different molecular sizes.28 Ethanethiol,
which has a molecular size smaller than the MOF cage, quenched
90% of the emission in about 3 h. In contrast, 2-amino-6-mercapto-
purine riboside, which is comparable in molecular size to the MOF
cavities, displayed a significantly slower quenching rate. A thiol-
terminated N-isopropylacrylamide/acrylic acid/t-butylacrylamide
copolymer gave rise to no detectable emission quenching. These
results highlight the ability of the MOF crystal to effectively
discriminate between quenching molecules of different sizes.
6. Concluding remarks and future
prospects
MOFs offer many advantages as platforms for the encapsula-
tion of NEs. Various effective strategies have been developed for
encapsulating almost every known type of functional NE with
a tunable structure in MOFs. NE@MOF composites not only
exhibit the properties of their individual constituents but can
also display synergistically enhanced properties. However, the
investigation of MOFs as hosts for the preparation of hybrid
composites is still in its infancy, and many challenges remain
to be addressed. In this section, we discuss the challenges that
we believe to be the most important.
(1) The accessibility of the encapsulated NEs has not been
well studied, in spite of extensive efforts devoted to developing
methods of incorporating NEs into MOFs. Owing to the micro-
structure of most MOF materials, high diffusion resistance
hinders the approach of reactants to the encapsulated active sites,
in particular, sites in the core of the MOF. The encapsulation of
NEs in yolk–shell MOFs is a promising solution to this problem.
The large voids in MOFs with this structure can significantly
accelerate the mass transfer of reactants and products by reducing
the diffusion length and increasing the concentration of reactants
This journal is © The Royal Society of Chemistry 2017

Tutorial Review
at the active sites. In addition, such MOFs provide sufficient
space to give the NEs a certain degree of freedom. To date, this
approach has only been used for metal NPs as guests.8,20,21
Studies of the fabrication of yolk–shell MOFs with other types
of NEs will undoubtedly be carried out in the future.
(2) Interactions at the interfaces between MOFs and NEs
Published on 18 May 2017. Downloaded by Indian Institute of Technology - Jammu on 7/13/2023 8:55:06 AM.
markedly affect the performance of NE@MOF composites.
Consequently, an understanding of these interactions is highly
desirable for establishing structure–property relationships. How-
ever, these interfaces tend to be ill defined, because stabilizing
agents are usually required for the synthesis of NE@MOF hybrid
composites. The synthesis of ‘‘naked’’ NEs within MOFs with
strong host–guest interactions is therefore highly desirable.
Furthermore, in-depth studies with the aim of characterizing
these interactions, in particular, by means of in situ and operando
methods, can be expected to improve our fundamental under-
standing of them and thus guide the design of the next generation
of high-performance NE@MOF composites.
(3) Combining different NEs within a single framework can
be expected to open new avenues to multifunctional materials.
For example, the combination of redox-active POMs (which can
undergo fast, reversible, and stepwise multi-electron trans-
formations) with photoactive molecular phosphors (which can
efficiently harvest sunlight) could enable synergistic excitation
by visible light and the facile injection of multiple electrons to
create more efficient visible-light-driven organic photocatalysts.
(4) Finally, although known NE@MOF composites exhibit
excellent performance, they can be fabricated only on the labora-
tory scale by means of low-yield time-consuming procedures.
Scalable low-cost methods for the preparation of advanced
composites are urgently required.
The rapid development of NE@MOF composites in the last few
years offers many new opportunities for the design of advanced
functional materials with versatile properties and applications.
Sustained research effort in this exciting area can be expected to
enable industrial applications in various fields that we envisage
will be part of future commercial ventures.
Acknowledgements
This work was supported by the NSF of China (21322606,
21436005, and 21576095), the State Key Laboratory of Pulp and
Paper Engineering (No. 2017ZD04), and the Guangdong NSF
(2013B090500027 and 2016A050502004).
Notes and references
1 H. R. Moon, D. W. Lim and M. P. Suh, Chem. Soc. Rev., 2013,
42, 1807–1824.
2 H. Deng, S. Grunder, K. E. Cordova, C. Valente, H. Furukawa,
M. Hmadeh, F. Gándara, A. C. Whalley, Z. Liu, S. Asahina,
H. Kazumori, M. O’Keeffe, O. Terasaki, J. F. Stoddartand and
O. M. Yaghi, Science, 2012, 336, 1018–1023.
3 G. Férey, C. Mellot-Draznieks, C. Serre, F. Millange, J. Dutour,
S. Surblé1 and I. Margiolaki, Science, 2005, 309, 2040–2042.
This journal is © The Royal Society of Chemistry 2017
View Article Online
Chem Soc Rev
4 J. Juan-Alcañiz, J. Gascon and F. Kapteijn, J. Mater. Chem.,
2012, 22, 10102–10118.
5 Q. L. Zhu and Q. Xu, Chem. Soc. Rev., 2014, 43, 5468–5512.
6 X. Li, T. W. Goh, L. Li, C. Xiao, Z. Guo, X. C. Zeng and
W. Huang, ACS Catal., 2016, 6, 3461–3468.
7 M. A. Nasalevich, R. Becker, E. V. Ramos-Fernandez,
S. Castellanos, S. L. Veber, M. V. Fedin, F. Kapteijn, J. N. H.
Reek, J. I. van der Vlugt and J. Gascon, Energy Environ. Sci.,
2015, 8, 364–375.
8 P. Hu, J. V. Morabito and C. K. Tsung, ACS Catal., 2014, 4,
4409–4419.
9 A. Dhakshinamoorthya and H. Garcia, Chem. Soc. Rev., 2012,
41, 5262–5284.
10 A. Aijaz and Q. Xu, J. Phys. Chem. Lett., 2014, 5, 1400–1411.
11 C. Rösler and R. A. Fischer, CrystEngComm, 2015, 17,
199–217.
12 C. R. Kim, T. Uemura and S. Kitagawa, Chem. Soc. Rev.,
2016, 45, 3828–3845.
13 P. Falcaro, R. Ricco, A. Yazdi, I. Imaz, S. Furukawa,
D. Maspoch, R. Ameloot, J. D. Evans and C. J. Doonan,
Coord. Chem. Rev., 2016, 307, 237–254.
14 L. Chen, H. Chen, R. Luque and Y. Li, Chem. Sci., 2014, 5,
3708–3714.
15 L. Chen, B. Huang, X. Qiu, X. Wang, R. Luque and Y. Li,
Chem. Sci., 2016, 7, 228–233.
16 B. Volosskiy, K. Niwa, Y. Chen, Z. Zhao, N. O. Weiss,
X. Zhong, M. Ding, C. Lee, Y. Huang and X. Duan, ACS
Nano, 2015, 9, 3044–3049.
17 Y. Liu and Z. Tang, Adv. Mater., 2013, 25, 5819–5825.
18 L. Chen, H. Chen and Y. Li, Chem. Commun., 2014, 50,
14752–14755.
19 H. Liu, L. Chang, C. Bai, L. Chen, R. Luque and Y. Li, Angew.
Chem., Int. Ed., 2016, 55, 5019–5023.
20 S. Wang, Y. Fan, J. Teng, Y. Z. Fan, J. J. Jiang, H. P. Wang,
H. Grützmacher, D. Wang and C. Y. Su, Small, 2016, 12(41),
5702–5709.
21 J. Yang, F. Zhang, H. Lu, X. Hong, H. Jiang, Y. Wu and Y. Li,
Angew. Chem., Int. Ed., 2015, 54, 10889–10893.
22 M. Zhao, K. Yuan, Y. Wang, G. Li, J. Guo, L. Gu, W. Hu,
H. Zhao and Z. Tang, Nature, 2016, 539, 76–80.
23 Z. Li and H. C. Zeng, Chem. Mater., 2013, 25, 1761–1768.
24 Z. Xu, W. Zhang, J. Weng, W. Huang, D. Tian and F. Huo,
Nano Res., 2016, 9, 158–164.
25 J. Aguilera-Sigalat and D. Bradshaw, Coord. Chem. Rev.,
2016, 307, 267–291.
26 D. Esken, S. Turner, C. Wiktor, S. B. Kalidindi, G. V.
Tendeloo and R. A. Fischer, J. Am. Chem. Soc., 2011, 133,
16370–16373.
27 K. Cho, S. H. Han and M. P. Suh, Angew. Chem., Int. Ed.,
2016, 55, 15301–15305.
28 P. Falcaro, A. J. Hill, K. M. Nairn, J. Jasieniak, James I. Mardel,
T. J. Bastow, S. C. Mayo, M. Gimona, D. Gomez, H. J. Whitfield,
R. Riccò, A. Patelli, B. Marmiroli, H. Amenitsch, T. Colson,
L. Villanova and D. Buso, Nat. Commun., 2011, 2, 237–244.
29 S. Saha, G. Das, J. Thote and R. Banerjee, J. Am. Chem. Soc.,
2014, 136, 14845–14851.
Chem. Soc. Rev., 2017, 46, 4614--4630 | 4629

Chem Soc Rev
30 W. Zhan, Q. Kuang, J. Zhou, X. Kong, Z. Xie and L. S. Zheng,
J. Am. Chem. Soc., 2013, 135, 1926–1933.
31 W. Zhang, G. Lu, S. Li, Y. Liu, H. Xu, C. Cui, W. Yan, Y. Yang
and F. Huo, Chem. Commun., 2014, 50, 4296–4298.
32 D. Y. Du, J. S. Qin, S. L. Li, Z. M. Su and Y. Q. Lan, Chem. Soc.
Rev., 2014, 43, 4615–4632.
Published on 18 May 2017. Downloaded by Indian Institute of Technology - Jammu on 7/13/2023 8:55:06 AM.
33 J. J. Ye and C. D. Wu, Dalton Trans., 2016, 45, 10101–10112.
34 R. Canioni, C. Roch-Marchal, F. Sécheresse, P. Horcajada,
C. Serre, M. Hardi-Dan, G. Férey, J. M. Grenèche, F. Lefebvre,
J. S. Chang, Y. K. Hwang, O. Lebedev, S. Turner and G. V.
Tendeloo, J. Mater. Chem., 2011, 21, 1226–1233.
35 X. Xu, Y. Lu, Y. Yang, F. Nosheen and X. Wang, Sci. China
Mater., 2015, 58, 370–377.
36 E. Kockrick, T. Lescouet, E. V. Kudrik, A. B. Sorokin and
D. Farrusseng, Chem. Commun., 2011, 47, 1562–1564.
37 J. V. Morabito, L. Y. Chou, Z. Li, C. M. Manna, C. A. Petroff,
R. J. Kyada, J. M. Palomba, J. A. Byers and C. K. Tsung, J. Am.
Chem. Soc., 2014, 136, 12540–12543.
38 B. Li, Y. Zhang, D. Ma, T. Ma, Z. Shi and S. Ma, J. Am. Chem.
Soc., 2014, 136, 1202–1205.
39 M. H. Alkordi, Y. Liu, R. W. Larsen, J. F. Eubank and
M. Eddaoudi, J. Am. Chem. Soc., 2008, 130, 12639–12641.
40 Z. Zhang, L. Zhang, L. Wojtas, M. Eddaoudi and M. J. Zaworotko,
J. Am. Chem. Soc., 2012, 134, 928–933.
4630 | Chem. Soc. Rev., 2017, 46, 4614--4630
View Article Online
Tutorial Review
41 M. B. Majewski, A. J. Howarth, P. Li, M. R. Wasielewski,
J. T. Hupp and O. K. Farha, CrystEngComm, 2017, DOI:
10.1039/c7ce00022g.
42 J. Mehta, N. Bhardwaj, S. K. Bhardwaj, K. H. Kim and
A. Deep, Coord. Chem. Rev., 2016, 322, 30–40.
43 P. Li, J. A. Modica, A. J. Howarth, E. Vargas L., P. Z. Moghadam,
R. Q. Snurr, M. Mrksich, J. T. Hupp and O. K. Farha, Chem.,
2016, 1, 154–169.
44 P. Li, S. Y. Moon, M. A. Guelta, S. P. Harvey, J. T. Hupp and
Omar K. Farha, J. Am. Chem. Soc., 2016, 138, 8052–8055.
45 D. Feng, T. F. Liu, J. Su, M. Bosch, Z. Wei, W. Wan, D. Yuan,
Y. P. Chen, X. Wang, K. Wang, X. Lian, Z. Y. Gu, J. Park,
X. Zou and H. C. Zhou, Nat. Commun., 2015, 6, 5979–5986.
46 K. Liang, R. Ricco, C. M. Doherty, M. J. Styles, S. Bell,
N. Kirby, S. Mudie, D. Haylock, A. J. Hill, C. J. Doonan
and P. Falcaro, Nat. Commun., 2015, 6, 7240–7247.
47 X. Qiu, W. Zhong, C. Bai and Y. Li, J. Am. Chem. Soc., 2016,
138, 1138–1141.
48 T. Uemura, N. Yanai and S. Kitagawa, Chem. Soc. Rev., 2009,
38, 1228–1236.
49 K. Fujie and H. Kitagawa, Coord. Chem. Rev., 2016, 307,
382–390.
50 Q. Yang, Q. Xu, S. H. Yu and H. L. Jiang, Angew. Chem.,
Int. Ed., 2016, 55, 3685–3689.
This journal is © The Royal Society of Chemistry 2017