Nano-Structures & Nano-Objects 14 (2018) 19–48

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Nano-Structures & Nano-Objects

journal homepage: www.elsevier.com/locate/nanoso

Transition metal oxide nanoparticles as efficient catalysts in oxidation

reactions
Ali Akbari a,b, *, Mojtaba Amini b, *, Abbas Tarassoli c, *, Bagher Eftekhari-Sis b ,
Naser Ghasemian a , Esmaiel Jabbari d
a
Faculty of Engineering, Department of Polymer Science and Engineering, University of Bonab, Bonab, Iran
b
Department of Chemistry, Faculty of Science, University of Maragheh, Maragheh, Iran
c
Department of Chemistry, College of Sciences, Shahid Chamran University, Ahvaz, Iran
d
Department of Chemical Engineering, University of South Carolina, Columbia, SC, United States

highlights graphical abstract

• A comprehensive review of transi-

tion metal oxide nanoparticles as
catalyst in oxidation reactions is pre-
sented in this article.
• This review is divided into eight
main sections based on the transi-
tion metal group number.
• Different synthesis methods of tran-
sition metal oxide nanoparticles and
their oxidation reaction conditions
are compared and summarized.

article info a b s t r a c t
Article history: Studies on nano-sized particles have been the range for the past 10–15 years. With rapid growth of metal
Received 10 November 2017 oxide nanotechnologies during the last decades, the application of this material in the field of catalysis
Received in revised form 8 January 2018 has become a substantial research area. In the past decades, the utilization of transition metal oxide
Accepted 20 January 2018
nanoparticle catalysts for industrial application in the synthesis of important chemical intermediates
has been investigated by industrial and academic communities. Compared to other catalysts, one of the
Keywords:
outstanding properties of metal oxide nanoparticles in catalysis is represented by the high selectivity
Nanoparticles
Metal oxide which allows discrimination within chemical groups and geometrical positions, favoring high yields of
Oxidation the desired product. This review is devoted to dealing with the application of transition metal oxide
nanoparticles as catalyst for oxidations of sulfides, alcohols, olefins, and alkanes toward the synthesis
of a variety of organic compounds, such as sulfoxides, aldehydes and ketones, carboxylic acids, epoxides
and alcohols.
© 2018 Elsevier B.V. All rights reserved.

* Corresponding authors.
E-mail addresses: ali.akbari@maragheh.ac.ir (A. Akbari), mamini@maragheh.ac.ir (M. Amini), tarassoli@scu.ac.ir (A. Tarassoli).

https://doi.org/10.1016/j.nanoso.2018.01.006
2352-507X/© 2018 Elsevier B.V. All rights reserved.
20 A. Akbari et al. / Nano-Structures & Nano-Objects 14 (2018) 19–48

Contents

1. Introduction......................................................................................................................................................................................................................... 20
2. Transition metal oxide nanoparticles ................................................................................................................................................................................ 20
2.1. Group 4 elements (Ti, Zr and Hf) ........................................................................................................................................................................... 20
2.1.1. Titanium oxide nanoparticles ................................................................................................................................................................ 20
2.2. Group 5 elements (V, Nb and Ta) .......................................................................................................................................................................... 24
2.2.1. Vanadium oxide nanoparticles .............................................................................................................................................................. 24
2.3. Group 6 elements (Cr, Mo and W) ........................................................................................................................................................................ 27
2.3.1. Molybdenum oxide nanoparticles......................................................................................................................................................... 27
2.3.2. Tungsten oxide nanoparticles ................................................................................................................................................................ 30
2.4. Group 7 elements (Mn, Tc and Re) ........................................................................................................................................................................ 31
2.4.1. Manganese oxide nanoparticles ............................................................................................................................................................ 31
2.5. Group 8 elements (Fe, Ru and Os) ......................................................................................................................................................................... 35
2.5.1. Iron oxide nanoparticles......................................................................................................................................................................... 35
2.6. Group 9 elements (Co, Rh and Ir) .......................................................................................................................................................................... 38
2.6.1. Cobalt oxide nanoparticles..................................................................................................................................................................... 38
2.7. Group 11 elements (Cu, Ag and Au) ...................................................................................................................................................................... 39
2.7.1. Copper oxide nanoparticles ................................................................................................................................................................... 39
2.8. Other metal oxides ................................................................................................................................................................................................. 45
2.8.1. Cerium oxide nanoparticles ................................................................................................................................................................... 45
3. Conclusion and outlook ...................................................................................................................................................................................................... 46
Acknowledgments .............................................................................................................................................................................................................. 46
References ........................................................................................................................................................................................................................... 46

1. Introduction an ongoing effort to miniaturize at the nanoscale processes that

Nowadays, oxidation reactions play a substantial role in mod-
ern chemistry as well as chemical industry. Around 30% of total
production in the chemical industry is carried out by the oxida-
tion process. It means that after polymerization, oxidation is the
largest process in the production of chemicals [1–12]. On the other
hand, many intermediates such as alcohols, epoxides, aldehydes,
ketones and organic acids are obtained via oxidation catalysis [2–
10,13–23]. From point of view of green and sustainable chemical
processing, oxidation reaction has been known as an important
reaction for enhancing the formation of selective products in com-
parison with non-selective reactions. On the other hand, in order
to increase the selectivity, optimization of the catalyst process
conditions are needed which satisfy the principles of green chem-
istry [24–27]. As a result, design and development of new catalytic
oxidation processes is essential for laboratories and industries.
As an example of green oxidation, the catalytic oxidation of
organic substrates to selective products has been known as one of
the most important chemical transformations in organic synthesis.
In this reaction, permanganate and dichromate were utilized as
traditionally oxidizing reagents but they are expensive, toxic and
generate to a large quantity of heavy-metal waste. Heterogeneous
catalytic systems use O2 or air as a simple and safe oxidant and
produce water as the sole by-product which not only solve the
above aforementioned problems but also follow the principles of
green and sustainable chemical processes [28–30]. Over the last
few years, considerable efforts have been devoted to the field of
nanotechnology [31–36] and nano-science especially at the inter-
face of metal and metal oxide nanoparticles (NPs) due to their
relatively high chemical activity as well as specificity of interaction.
These nano-sized materials in comparison to their bulk equivalents
have many different properties such as a large surface-to-volume
ratio [37]. Among all the materials to be prepared on the nanoscale,
transition metal oxides are noteworthy candidates from a scientific
as well as a technological point of view [38,39]. Transition metal
oxides can exhibit unique characteristics which make them the
most versatile class of materials with properties covering all as-
pects of solid state and materials science [40]. Oxidation reactions
catalyzed by transition metal oxide NPs have recently evolved as
a major research direction of our modern society resulting from
currently use Microsystems. Toward this end, an updated com-
prehensive review on transition metal oxide NPs for catalysis of
oxidation reactions has not been published until now. The focus
of this review is to discuss the scope and limitations of transition
metal oxide NPs as an efficient catalyst for the oxidation of various
organic substrates, such as olefins, alcohols, alkanes and sulfides.
However the application of transition metal oxides as a support
is not covered here. Consequently, this review mainly covers the
literature published during the past 20 years and is divided into
eight main sections based on the transition metal group number.
In each section, the articles are chronologically ordered according
to metal type.
2. Transition metal oxide nanoparticles
2.1. Group 4 elements (Ti, Zr and Hf)
2.1.1. Titanium oxide nanoparticles
TiO2 NPs are well known as a photocatalyst and have been
widely utilized for photochemical applications such as, degrada-
tion of organic and inorganic pollutants [41,42], solar cells [43,44],
organic transformations and hydrogen production by water split-
ting [45]. Oxidation reactions as an important organic transforma-
tion using TiO2 NPs have attracted much attention. In most cases,
TiO2 NPs were used as photo-degradation materials.
2.1.1.1. Alcohols oxidation. Although TiO2 NPs have photo-degra-
dation capacity, a significant volume of research has been recently
carried out in selective oxidation of organic substrates such as
alcohols, amines, aromatic alkanes and cyclohexanes by TiO2 in
the presence of O2 under UV–Vis irradiation. For instance, a green
oxidation method was developed for the oxidation of secondary
alcohols to corresponding ketones by Kidwai and coworkers [46].
In this protocol, TiO2 NPs were used as a heterogeneous catalyst in
the presence of polyethylene glycol (PEG 400) as a green solvent
and H2 O2 as an oxidative regent. For the possible reaction mecha-
nism, they proposed the production of superoxide species O−2 over
TiO2 NPs. As it can be seen from Fig. 1, free radicals can be formed
via reaction of reactive O−2 with alcohols, leading to the desired
products.
 A. Akbari et al. / Nano-Structures & Nano-Objects 14 (2018) 19–48
Fig. 1. Plausible reaction mechanism for alcohol oxidation over TiO2 nanoparticles [46].
Three different primary cyclohexyl alcohols were oxidized by
TiO2 NPs illuminated for 20 h using 450 W medium pressure
mercury lamp. Photocatalytic oxidation by TiO2 showed different
conversion ratios depending on the type of cyclohexyl alcohol
used [47]. Suggested mechanism was the formation of electron–
hole pair at the surface of TiO2 NPs followed by oxidation reaction.
Single crystalline rutile TiO2 nanorods were used as an effective
photocatalyst for selective oxidation of benzyl alcohol into ben-
zaldehyde. Rutile TiO2 nanorods were prepared via hydrothermal
method in which the hydrothermal reaction time affected the
crystallite size of TiO2 nanorods. For example, the crystallite size
of as-prepared nanorods was 19.9 nm and 25.5 nm when the
hydrothermal reaction time was 4 and 24 h, respectively. By con-
trolling the hydrothermal reaction time, it was possible to optimize
the surface properties of TiO2 nanorods which had a remarkable
effect in obtaining higher selective photocatalytic activity [48].
The catalytic activity of TiO2 nanorods for selective oxidation of
benzyl alcohol was compared with TiO2 NPs. Results showed that
the former was more active because of its high surface-to-volume
ratio which facilitated the interaction, adsorption and desorption
of organic molecules with the surface.
Selective photocatalytic oxidation of benzyl alcohol and its
derivatives into their carbonyl products (up to 99% in selectivity
and conversion) was fully studied over TiO2 NPs under visible-light
by Higashimoto and coworkers [49–51]. From these studies, the
authors verified the existence of the interaction between benzylic
alcohol compounds and the surface of TiO2 NPs. On the other hand,
the interaction of –CH2 OH group or phenyl ring of benzyl alcohol
with surface hydroxyl groups led to the formation of a surface
complex which induced absorption in the visible region. These
interactions were depicted in Fig. 2.
After irradiation with visible light, the surface complex was
photo-excited and produced holes (h+ ) which abstracted hydrogen
atoms from CH2 OH group of benzyl alcohol. In this process, oxygen
molecules not only played a remarkable role as an electron accep-
tor but also they regenerated the hydroxyl groups on TiO2 surface
and increased the rate of selective oxidation of benzyl alcohol.
A similar photo-oxidation mechanism was reported for methanol
over rutile TiO2 NPs [52].
Recently, one dimensional TiO2 nanomaterials or nanobelts
have gained attention as photocatalysts due to their larger surface-
to-volume ratio and the lower number of grain boundaries [53],
but they have some critical drawbacks such as poor visible light
utilization, fewer surface active sites and most importantly the
high recombination of photo-generated electron–hole pairs which
remarkably limits their practical applications [54]. Assembling the
second phases on the 1D TiO2 nanostructures can solve the afore-
mentioned problems. For instance, a simple synthetic protocol was
21
developed for fabrication of RuO2 /TiO2 nanobelt heterostructures
using a co-precipitation method [55]. Well dispersion of RuO2 NPs
with an average size of 2.4 ± 0.5 nm over the TiO2 nanobelt surface
caused the formation of RuO2 /TiO2 which acted as an efficient pho-
tocatalyst in the oxidation of benzyl alcohol under UV and visible
light irradiation compared with the individual RuO2 NPs and TiO2
nanobelt. Experimental results showed 98, 70 and 55% selectivity
for benzyl alcohol oxidation over RuO2 /TiO2 nanobelt heterostruc-
tures, TiO2 nanobelt, and RuO2 NPs, respectively. This high catalytic
activity of RuO2 /TiO2 nanobelt heterostructures could be related to
the energy band matching between RuO2 and TiO2 as well as the
ability for separation of photo-generated electron–hole pairs.
Mesoporous materials can be considered as promising com-
pounds due to their three-dimensional network and large accessi-
ble pore surface [56,57]. In this approach, a facile and simple syn-
thesis of nanostructured titania using a surfactant-assisted aggre-
gating assembly of TiO2 NPs was reported [58,59]. The as-prepared
TiO2 NPs possessed a high-surface-area but they had a wide band
gap electron transition (Eg ∼ 3.2 eV). By interconnecting of CdS
quantum dots (ca. 5–6 nm) in the structure of mesoporous TiO2
NPs (ca. 8 nm), it was possible to decrease the wide band gap
electron transition to ∼2.5 eV. The CdS–mesoporous TiO2 NPs, as a
heterostructured catalyst, showed excellent photocatalytic activity
for the oxidation of various para-substituted aromatic alcohols
into the corresponding carbonyl compounds under UV–visible ir-
radiation using molecular oxygen as an oxidant. All alcohols were
converted to the desired carbonyl compounds with up to 99% se-
lectivity. The high selectivity could be related to the large internal
surface and narrow pore size distribution of NPs in the structure of
the catalyst.
TiO2 NPs were embedded into the three different allotropes
of carbon, namely Graphene (GR), carbon nanotubes (CNT) and
fullerene (C60 ) using a sol−gel process along with hydrothermal
post-treatment [60]. Selective photo-oxidation of benzyl alcohol to
benzaldehyde was employed as a probe reaction to investigate the
photocatalytic activity of as-prepared nanocomposites under visi-
ble light irradiation. Experimental results showed an efficient cat-
alytic performance for all nanocomposites. Existence of carbon ma-
terials not only extended the adsorption edge of all TiO2 −carbon
nanocomposites to the visible light region, but also increased the
lifetime of photo-generated electron−hole pairs. These positive
effects could be related to their high catalytic activity. The same
authors synthesized TiO2 - GR and TiO2 -CNT nanocomposites by a
simple random integration of solid TiO2 particles with these carbon
materials [61]. The photocatalytic activity of as-prepared catalysts
was tested in the oxidation of various benzylic alcohols.
In another report, core–shell AgBr@TiO2 NPs were immobi-
lized onto the surface of graphene oxide (GO) and utilized as a
22 A. Akbari et al. / Nano-Structures & Nano-Objects 14 (2018) 19–48

Fig. 2. Possible reaction mechanism for the selective photo-oxidation of benzyl alcohol over TiO2 under visible light irradiation [50].

Fig. 3. Schematic illustration for charge separation of AgBr@TiO2 /GO under visible light irradiation [62].

ternary nanocomposite photocatalyst, AgBr@TiO2 /GO for the selec-
tive oxidation of benzyl alcohol under visible light irradiation [62].
The results showed that the AgBr@TiO2 /GO ternary composite
exhibited superior photocatalytic activity compared with AgBr,
AgBr@TiO2 , and AgBr/GO. Photoluminescence analysis confirmed
that anchoring AgBr@TiO2 onto GO caused the highest separa-
tion rate of photo-generated electrons and holes. Photocatalytic
oxidation mechanism was depicted in Fig. 3. As it could be seen
from Fig. 3, GO, with excellent conduction property, not only could
further transfer electrons but also facilitate their trapping by ad-
sorbed oxygen.
In 2013, Wang and colleagues synthesized new single-crystal
TiO2 with 2D and 3D ordered mesoporous structures and exposed
(001) facets via solvothermal method using SBA-15 or KIT-6 and
TiOSO4 as hard template and titanium precursor, respectively [63].
The catalytic activity of as-prepared materials was investigated
for photo-oxidation of various alcohols under UV-irradiation and
the results were compared with polycrystalline TiO2 of a similar
 A. Akbari et al. / Nano-Structures & Nano-Objects 14 (2018) 19–48
Fig. 4. A plausible mechanism of photocatalytic selective oxidation [63].
mesoporous structure. Experimental results revealed that the TiO2
with 3D ordered mesoporous structure exhibited high catalytic
activity due to its high light harvesting ability as well as reducing
the recombination rate between photoelectrons and holes. Authors
proposed a simple reaction mechanism in Fig. 4 by UV light ir-
radiation, the TiO2 semiconductor produced photoelectrons (e− )
and holes (h+ ). Photogenerated holes and electrons are responsible
for the activation of adsorbed alcohol to produce alcohol cation
radicals and O2 to form . O− 2 radicals, respectively. At the end, the
. −
O2 radicals reacted with alcohol cation radicals to produce desired
product.
Two types of TiO2 and SiO2 /TiO2 (7% Si/Ti) were synthesized
using a sol–gel method through the hydrolysis of titanium (IV)
n-butoxide followed by calcination at 430 ◦ C [64]. The catalytic
activity of as-prepared materials was tested for selective oxidation
of benzyl alcohol. Experimental results showed similar selectivity
(98%) for both catalysts with 42% and 46% alcohol conversion for
TiO2 and SiO2 /TiO2 , respectively. Moreover, other experimental
Fig. 5. Proposed reaction mechanism for photo-oxidation of alcohols over TiO2 nanoparticles [64].
23
Fig. 6. Disproportionate decomposition of the side-on peroxide under UV irradia-
tion [64].
results demonstrated that TiO2 and SiO2 /TiO2 photocatalysts pre-
treated with various acids significantly promoted the conversion
of benzyl alcohol to benzaldehyde (91% and 66% conversion over
acid pretreated SiO2 /TiO2 and TiO2 , respectively). So in order to find
the effect of protons (bronsted acid) on the oxidation reaction, a
cyclic reaction mechanism was proposed according to the analysis
of experimental results. As illustrated in Fig. 5, the generation of
intermediate 4 with side-on peroxide was evidenced by using 18 O
labeling and Raman spectroscopy [65].
The intermediate 4 could be easily decomposed with acids to
regenerate the TiO2 based catalyst. On the other hand, protons
significantly accelerate the disproportionate decomposition of the
side-on peroxide as depicted in Fig. 6.
Stronger adsorption of organic compounds on the surface of
individual TiO2 NPs would lead to an increase in the amount of
oxidation products and facilitate the photocatalytic decomposition
of products, followed by a decrease in reaction selectivity. For
example, when the photo-oxidation of benzyl alcohol was carried
out over pure TiO2 NPs in water, the benzaldehyde selectivity de-
creased with photo-irradiation time. This indicated that pure TiO2
NPs decomposed the benzaldehyde and formed CO2 as by-product.
The suppression of benzaldehyde adsorption onto the TiO2 surface
is one possible way to enhance benzaldehyde selectivity. In this
approach, partial coating of TiO2 with WO3 NPs was reported by
Tsukamoto et al. [66]. With this system (WO3 (7.6)/TiO2 ), they
24 A. Akbari et al. / Nano-Structures & Nano-Objects 14 (2018) 19–48
(A) TiO2 .
(B) WO3 /TiO2 .
Fig. 7. Schematic illustration of benzyl alcohol oxidation on the surface of (A) TiO2 and (B) WO3 /TiO2 [66].
increased the selectivity of title reaction for 4-methoxybenzyl al-
cohol from 23% over pure TiO2 NPs to 50%. Fig. 7 shows the reaction
mechanism on the surface of catalysts. As shown in Fig. 7, the
overoxidation and decomposition of benzaldehyde occurred on the
surface of pure TiO2 NPs. In contrast, WO3 NPs acted as inactive
sites and inhibited the decomposition of benzaldehyde to CO2 .
The oxidation of various organic compounds over TiO2 catalysts
is also possible without light irradiation. In one report, various
metal ions were incorporated in the structure of TiO2 NPs using
a simple co-precipitation method at room temperature [67]. As-
prepared metal ion doped TiO2 NPs (M–TiO2 , M = Cr3+ , Mn2+ ,
Fe3+ , V5+ , Zn2+ , Ni2+ , Ag+ , Cu2+ and Co2+ ) were utilized for the
oxidation of benzyl alcohol, styrene and toluene without light
irradiation in the presence of tert-butyl hydroperoxide (TBHP) as
an oxidant. The catalytic behavior of M–TiO2 could be tuned by
changing the metal ion, doping amount, and calcination temper-
ature. Experimental results revealed that in the case of styrene
oxidation, Cu–TiO2 (58 nm) and Co–TiO2 (67 nm) showed higher
catalytic activity with 10 and 15 mol% loading of Cu and Co,
respectively. In addition, Co–TiO2 (20 mol% Co) and Cu–TiO2 (15
mol% Cu) exhibited the highest catalytic activity in the oxidation
of benzyl alcohol and toluene toward chlorine-free benzaldehyde,
respectively.
Recently, our research group synthesized a series of vana-
dium doped TiO2 NPs using titanyl nitrate and ammonium meta-
vanadate as starting materials by a one-pot solution combustion
method [68]. The oxidation of benzyl alcohol was selected as a
model reaction in order to evaluate catalytic activity of as-prepared
catalysts. After evaluation of various parameters, maximum activ-
ity of catalyst (97% conversion and 88% selectivity) was achieved
using TiO2 /V15 (V: 0.15 mol%), H2 O2 as an oxidant and methanol as
a solvent. Beside the oxidation of various alcohols, the synthesized
catalyst showed high catalytic performance for the oxidation of
different substituted olefins. In addition, the catalyst could be
recycled 5 times and no significant loss of activity was observed.
It should to be noted that the benzyl alcohol conversion was very
low in the absence of catalyst or H2 O2 by using the TiO2 /V15/H2 O2
system. This phenomenon encouraged us to propose a free radical
mechanism for the title reaction. The reaction mechanism is illus-
trated in Fig. 8.
The proposed mechanism was further verified by the addition
of 2,6-di-tert-butyl-p-cresol as a radical scavenging agent in this
process. When 2,6-di-tert-butyl-p-cresol (0.01 mmol) was added
as a radical scavenger, the oxidation was strongly suppressed. The
same catalytic system was prepared and utilized for the oxidation
of different sulfides into the corresponding sulfoxides [69].
TiO2 nanomaterials with different crystalline structures and
surface morphologies, TiO2 NPs (TiO2 NPs), TiO2 nanotubes (TiO2
NTs) and TiO2 nanofibers (TiO2 NFs) were directly utilized for the
selective oxidation of hydrocarbon materials under mild, solvent-
free conditions [70]. A mean diameter of 1.6 ± 0.4 nm, 60.5 ± 7.0
nm and 138.3 ± 1.2 nm was reported for TiO2 NPs, TiO2 NTs
and TiO2 NFs, respectively using TEM analyses. Catalytic results
demonstrated that TiO2 NFs showed slightly better activity com-
pared to the other catalysts tested due to the dominancy of rutile
phase in TiO2 NFs.
A green protocol was developed for the oxidation of 5-(Hydroxy
methyl)-2-furaldehyde (HMF) to 2,5-furandicarbaldehyde in the
presence of home-made anatase, rutile, and brookite TiO2 NPs in
aqueous media [71]. This method provided a fully environmentally-
friendly photocatalytic process which converted the common
industrial by-product 5-(Hydroxymethyl)-2-furaldehyde into the
useful corresponding aldehyde. In addition, the five-membered
ring HMF, which is less stable compared to other aromatic six-
membered ring molecules decomposed to many hydroxylated
species during the photocatalytic oxidation process. Interestingly,
experimental results showed the absence of other oxidized species
in solution throughout this process. Fig. 9 presents the plausible
reaction mechanism. As shown in Fig. 9, the rate-determining step
involved the formation of alcoholic group by either a hole (h+ ) or
a hydroxyl radical, followed by conversion to the aldehyde group.
2.2. Group 5 elements (V, Nb and Ta)
2.2.1. Vanadium oxide nanoparticles
Direct use of vanadium oxide NPs in the oxidation reactions
is rare. In most cases, vanadium oxide NPs are supported on the
 A. Akbari et al. / Nano-Structures & Nano-Objects 14 (2018) 19–48 25

Fig. 8. Possible oxidation mechanism of benzyl alcohol over TiO2 /V15 catalyst [68].

Fig. 9. Hypothesized mechanism for HMF oxidation to FDC over TiO2 nanoparticles [71].

surface of other metal oxides and the nature of support affects the
catalytic activity of vanadium NPs.
Oxidation of propene to propene oxide is difficult by vanadium
oxide NPs due to the formation of other products such as ethanal,
acrylaldehyde and propanal. In one report [72], using a flow re-
actor system instead of a closed system enabled investigators to
decrease the contact time between the substrate and catalyst and
subsequently suppressed decomposition of the unstable propene
oxide intermediate. In this method, the silica-supported vanadium
oxide catalyst (V2 O5 /SiO2 ) was synthesized and used in the photo-
epoxidation of propene. In addition, catalyst loading amount and
the effect of wavelength was examined. Experimental results
showed that the highest propylene oxide selectivity was obtained
with 0.18 wt% loaded catalyst at wavelengths less than 380 nm.
Fig. 10 depicts the proposed mechanism of the photo-oxidation
of propene over V2 O5 /SiO2 under irradiation in the presence of
oxygen molecules. Fig. 10. Photo-oxidation mechanism of propene over V2 O5 /SiO2 under irradia-
tion [72].
In this mechanism, well dispersion of VO4 tetrahedra on the
silica was crucial to the photo-oxidation of propene to propene
oxide. On the other hand, with the highly loaded V2 O5 /SiO2 , V5+
species were aggregated and caused isomerization of propylene ways to find the isolated monovanadates, surface polyvanadates,
oxide to propionaldehyde. and bulk vanadia on most oxide supports [74]. Analytical results
In another report [73], V2 O5 was supported on the surface of showed that both kinetic parameters and the first order rate-
Al2 O3 (V2 O5 /Al2 O3 ) and used as a catalyst for the oxidation of constant for breaking the C–H bond were independent of surface
methanol toward formaldehyde as a carbonyl product. In order to acidity and surface species concentrations, respectively. Recently,
elucidate the mechanism of methanol oxidation reaction as well the effect of supports with different compositions on the catalytic
as determination of kinetic parameters like Kads , Krds and TOF, activity of vanadium oxide NPs was investigated. It is worth noting
different spectroscopic techniques such as Raman, temperature- that the existence of support led to the formation of new active
programmed surface reaction (TPSR) and UV–Vis diffuse reflection vanadium sites like isolated monovanadates, surface polyvana-
spectroscopy (DRS) were utilized. These techniques provided easy dates, and bulk vanadia, depending on the vanadia coverage and
26 A. Akbari et al. / Nano-Structures & Nano-Objects 14 (2018) 19–48
pretreatment conditions. In addition, oxygen binding strengths
in the vanadia played a crucial role during the oxidation process
which was affected by the interaction with support [75]. For in-
stance, vanadia was immobilized onto alumina, zirconia and titania
supports using impregnation method. In one study, these catalytic
systems were utilized in the oxidation of methanol [76]. The effect
of oxygen binding on the catalytic activity of each material was
investigated by coulometric titration. For all supported vanadia
catalysts, methanol oxidation was carried out with 90% selectivity
toward formaldehyde. However, for V2 O5 /Al2 O3 the major prod-
uct was dimethyl ether at the highest temperature. Experimental
results also demonstrated that this reaction followed a Mars–van
Krevelen mechanism.
In another report, the same catalytic systems were used in
selective oxidation of formaldehyde to formic acid [77]. Results
for formaldehyde oxidation showed that formic acid formation
occurred on the vanadia species and methyl formate formed
on the free area of support. Additionally, compared to other
supported-vanadia catalysts, V2 O5 /TiO2 showed the highest activ-
ity on those surfaces having oligomeric vanadium species. Vana-
dium and molybdenum oxide particles were supported on the
surface of alumina and titania by Heracleous and coworkers [78]
and used in the oxidative dehydrogenation (ODH) of ethane and
propane. Many factors such as the effect of active metal oxide, the
effect of support and the effect of alkane were studied in more
details. Results indicated that molybdena catalysts were less active
than vanadia catalysts in the oxidative dehydrogenation of ethane
and propane, irrespective of the support used. Moreover, titania-
supported catalysts were more active and less selective than those
supported on alumina, indicating the great influence of support
on catalytic activity. Beside the above supported metal oxides, the
nanometer CeO2 was also used as a support in vanadia catalyst [79].
CeO2 NPs were synthesized using microwave-assisted heating hy-
drolysis, then vanadia catalysts with different vanadium loadings
were supported on CeO2 NPs via the incipient-wetness impreg-
nation method. The catalytic performance of as-prepared catalyst
was studied in the oxidation of soot. The amount of vanadium
loaded had a substantial effect on the structure of catalysts. On
the other hand, isolated mono-vanadate species, poly-vanadate
species and CeVO4 crystallites were formed at low, medium and
high vanadium loading, respectively. Additionally, the experimen-
tal results showed that the poly-vanadate species were more active
than mono-vanadate species and CeVO4 for soot oxidation and the
nanometer size effect of CeO2 also increased the catalytic activity
of vanadia catalysts by increasing the contact between the catalyst
and soot.
In the past decades, tremendous efforts have been made in the
selective oxidation of cyclohexane because among the oxidation
products, cyclohexanone is an essential intermediate in the pro-
duction of nylon-6,6. Research survey showed that vanadium oxide
NPs were used as catalysts in the oxidation of cyclohexane. As men-
tioned above, vanadium oxide NPs are supported on the surface of
other metal oxides in order to improve their catalytic performance.
The type of support for oxide materials affected the molecular
structure of the vanadium oxide spices. In one study [80], three dif-
ferent supports, namely Al2 O3 , SiO2 and TiO2 , were utilized in the
synthesis of vanadium oxide based catalysts using wet impregna-
tion and grafting as two different synthetic methods. The catalytic
behavior of as-synthesized catalysts was fully investigated in the
oxidation of cyclohexane. For this purpose, the effect of various
parameters such as vanadium distribution, reaction time, oxidant
concentration, catalyst amount and co-catalyst concentration were
studied. Experimental results demonstrated that vanadium oxide
NPs supported on TiO2 had maximum activity compared to other
catalysts and gave a mixture of products. Moreover, pyrazine 2-
carboxylic acid (PCA) as co-catalyst had a crucial role in the ox-
idation of cyclohexane which accelerated the production of hy-
droxyl radicals in the presence of hydrogen peroxide [81]. In 2010,
the same authors synthesized MgO particles and used as support
for the preparation of vanadium oxide NP catalyst via grafting
and impregnation methods [82]. The catalytic performance of as-
prepared catalysts was evaluated for the liquid-phase oxidation of
cyclohexane. Different parameters such as reaction time, catalyst
amount, vanadium loading as well as hydrogen peroxide concen-
tration were studied. The method of preparation and the amount
of vanadium loading had remarkable effects on the structure of
prepared catalysts. For example, the oxidation of cyclohexane was
not considerable for impregnated or grafted MgO-supported vana-
dium oxide catalysts with low vanadium loading which consisted
of isolated VO4 spices. Conversely, new phases like ortho-Mg3 V2 O8 ,
pyro-Mg2 V2 O7 and meta-MgV2 O6 were formed in the structure of
the catalysts by increasing the amount of vanadium loading, which
in turn exhibited high conversions ranging from 40 to 67% for the
oxidation of cyclohexane. In all cases explained above, a mixture
of products was obtained after oxidation of cyclohexane. In order
to increase the cyclohexanone/cyclohexanol molar ratio in the
oxidation of cyclohexane, recently Yang and coworkers developed
a new V2 O5 @TiO2 catalyst by deposition of vanadium spices on
TiO2 [83]. The prepared catalyst exhibited high selective aerobic
oxidation of cyclohexane to cyclohexanone under simulated solar
light irradiation. The effect of various parameters such as solvent,
reaction time, oxygen pressure, amount of vanadium spices de-
posited on TiO2 was investigated. Among them, different solvents
as well as the amount of vanadium spices had remarkable influ-
ence on photocatalytic oxidation of cyclohexane. In another word,
when methylene dichloride/water and n-hexane/water were used
as the solvents, both conversion and selectivity were low. Con-
versely, high selectivity (nearly 100%) was obtained using acetoni-
trile/water as the reaction solvent by volume ratio of 10/1. In the
case of amount of vanadium loading, 0.003 to 0.07 g of catalyst
(V2 O5 /TiO2 ) was examined. Experimental results demonstrated
that 0.01 g of catalyst (0.01–V2 O5 /TiO2 ) showed highest conversion
and cyclohexanone/cyclohexanol molar ratio. It is worth to men-
tion that the conversion and ketone/alcohol molar ratio decreased
when the vanadium content of the catalyst was more than 0.01 g
because of the agglomeration of vanadium spices on the surface
of TiO2 . The optimum reaction condition was obtained using ace-
tonitrile/water as the reaction solvent, 0.01 g of V2 O5 /TiO2 , 2.0 MPa
oxygen pressure and a reaction time of 8 h. The proposed mecha-
nism is illustrated in Fig. 11. At first, the reactants were adsorbed
on the surface of V2 O5 /TiO2 as catalyst. Then the electron (e− ) and
positive hole (h+ ) pairs were produced under simulated solar light
irradiation. Subsequently, the generated holes oxidized water and
produced H+ and − OH. At the same time, the generated electrons
reduced V5+ to V4+ which could easily release and transfer the
electron to O2 absorbed on the catalyst surface to produce O·− 2 .
In order to improve the conversion of cyclohexane oxidation
reaction, for the first time, a hetero-mixed of vanadium oxide NPs
with WO3 as the catalyst was designed and synthesized [84]. The
hetero-mixed catalyst (V2 O5 /WO3 ) was obtained using ethylene
glycol and polyvinylpyrrolidone (PVP) as solvent and templating
agent, respectively, followed by calcination at 500 ◦ C for 4 h. For
comparison, the individual catalysts, V2 O5 and WO3 , were synthe-
sized according to the same procedure. The catalytic activity of all
as-prepared catalysts was evaluated for the oxidation of cyclohex-
ane at room temperature in the presence of H2 O2 . Experimental re-
sults demonstrated that the conversion efficiency of catalysts was
increased in the order of V2 O5 /WO3 > WO3 > V2 O5 . According to
this finding, it is clear that the combination of two metal oxides had
a synergic influence which facilitated the electron charge transfer
between metals, leading to improved oxidation rates. Controlled
decomposition of H2 O2 into reactive radicals can be assumed as
a key point of this reaction. In this approach, the hetero-mixed
V2 O5 /WO3 catalyst enhanced the rate of H2 O2 decomposition. This
 A. Akbari et al. / Nano-Structures & Nano-Objects 14 (2018) 19–48 27

Fig. 11. Possible photo-oxidation mechanism of cyclohexane over V2 O5 /TiO2 [83].

Fig. 12. Possible products from liquid phase oxidation of cyclohexane [84].

research showed that many parameters such as catalyst amount,
reaction time and catalyst stability had a significant influence on
the conversion and selectivity of cyclohexane oxidation reaction.
Increasing the catalyst amount had a positive effect on reaction
conversion. For instance, in the case of using 25 mg of catalyst,
the conversion was 30% while conversion reached 71% at 100
mg of catalyst. As it can be seen from Fig. 12, the known over-
oxidation products included adipic acid, 6-hydroxyhexanoic acid
and ε -caprolactone can be formed by increasing the reaction time.
These by-products had dropped the selectivity of the reaction
remarkably to 63%.
2.3. Group 6 elements (Cr, Mo and W)
2.3.1. Molybdenum oxide nanoparticles
Among the known transition metal oxides, molybdenum oxides
(MoOx ) have attracted significant research interest due to their
unique structural characteristics. MoOx has two simple binary
oxides as MoO2 and MoO3 . Molybdenum oxides (MoOx ) have been
broadly utilized in the field of sensors [85], electrode materials [86]
and recording materials [87]. However the catalytic activity of
these NPs has been reported less than other applications. In most
cases, molybdenum dioxide, MoO2 , has been used as the catalyst
in cracking and reforming of hydrocarbon compounds [88,89].
Recently, Bento and coworkers reported novel MoO2 NPs as
efficient catalysts in epoxidation of olefins [90]. Commercial MoO3
was used as starting material for the synthesis of tremella-like
HQ
MoO2 NPs in the presence of ethylenediamine and hydro-
quinone as reducing and assisting agents, respectively. The key
point of this study was the use of hydroquinone instead of iron
oxide [91] which allowed monitoring the sole role of MoO2 in the
epoxidation of olefins. The catalytic application of as-synthesized
MoO2 NPs was tested in the epoxidation of two sets of olefins
namely simple olefins and multifunctional olefins. In order to
find the optimized reaction conditions, different oxygen donors
tert-butyl hydroperoxide (TBHP) or cumene hydroperoxide (CHP),
28 A. Akbari et al. / Nano-Structures & Nano-Objects 14 (2018) 19–48

solvents (acetonitrile and toluene) and temperatures 353 and 383

K were tested. Experimental results about simple olefins showed
that they were converted to their corresponding epoxides in the
presence of TBHP with good selectivity. For example, 100% con-
version and selectivity was obtained in the epoxidation of cis-
cyclooctene in toluene at 383 K. however, in the case of styrene,
the conversion was 93% with low selectivity for the same con-
dition. Capability of HQ MoO2 NPs in chemoselective epoxidation
reaction was also evaluated using a more sensitive olefin like R-(+)-
limonene with two unsaturated double bonds. Only one epoxide
isomer, endo cyclic, was obtained. Moreover, the catalyst was
recoverable with high catalytic activity after three runs.
In another work, the same authors developed new tremella-like
molybdenum dioxide NPs, Fe-doped MoO2 , for epoxidation of the
same olefins [92]. In this study, Fe-doped MoO2 was synthesized
by a hydrothermal method according to the reported procedure
with slight modification [90]. In the modified synthesis, Fe2 O3
was utilized as the assisting agent instead of hydroquinone. This
assisting agent not only acted as a nucleation core for the growth
of MoO2 NPs but also regenerated the oxidized ethylenediamine
during synthesis. Catalytic performance of as-prepared Fe-doped
MoO2 NPs were tested in olefin epoxidation with the aim of inves-
tigating the effect of catalyst on product selectivity. In this regard,
many different parameters such as olefin derivative, solvent, oxi-
dant reagent and temperature were studied in detail. Experimental
results in terms of both olefin conversion and product yield showed
similar performance as the HQ MoO2 NPs counterpart. There were
some major differences between Fe-doped MoO2 and HQ MoO2 NPs
as catalysts. One difference was observed in the case of styrene
epoxidation in which the selectivity of HQ MoO2 for styrene epoxide
was much higher than Fe-doped MoO2 NPs. Conversely, the in-
duction period for the kinetics of cis-cyclooctene oxide formation
Fig. 13. Preparation route of HM-Mo catalyst [96].
was 2 and 8 h for Fe-doped MoO2 and HQ MoO2 NPs as catalysts,
respectively. This low induction period can be attributed to the
positive effect of Fe2 O3 . It is worth to mention that in some cases,
Fe-doped MoO2 showed no induction periods at all compared to coating layer was dense silica/mesoporous silica, 99% conversion
compare to HQ MoO2 . was obtained. While in the case of dense silica, only 37% olefin
Another interesting magnetically separable MoO2 NP based cat- conversion was achieved. This result revealed that materials with a
alyst was developed by Shokouhimehr and coworkers [93]. In this mesoporous structure and high surface area showed high catalytic
research, uniform hematite (α -Fe2 O3 ) NPs were prepared as a core activity (352 m2 g−1 ) and in comparison with dense silica (surface
with an average size of 400 nm via hydrothermal method, followed area = 23 m2 g−1 ).
by the deposition of a dense silica layer with thickness of 50 nm Survey of the articles showed that Molybdenum (VI) complexes
on its surface. The next step involved the formation of another bearing organic ligands acted as homogeneous catalysts in most
mesoporous silica shell using sol–gel polymerization of a mix- organic transformation [94,95]. In one report, two types of Molyb-
ture of tetraethoxysilane (TEOS) and n-octadecyltrimethoxysilane denum (VI) catalysts with different structures were synthesized
(C18TMS) at room temperature for 2 h. The as-prepared nanocom- and used for the liquid phase epoxidation of olefins [96]. In that
posite was calcined at 500 ◦ C for 5 h to remove the organic groups. study, [Mo(O)2 Cl2 ] was grafted on a new hybrid mesoporous ma-
Finally, MoO2 NPs were produced by impregnation of ammo- terial. The overall synthetic route is illustrated in Fig. 13.
nium molybdate into the mesoporous structure of as-synthesized As it could be seen from Fig. 13, the first stage of the syn-
thesis of hybrid mesoporous (HM) support included a simple co-
nanocomposite, followed by the reduction in a flowing mixture
condensation of two different organosilanes in the presence of
of H2 and N2 (1:1) at 500 ◦ C for 12 h. As a probe reaction, cis-
Pluronics P123 as a template. The next steps consisted of chemi-
cyclooctene was utilized as substrate in the epoxidation reaction
cal removal of template, followed by oxidation of the phosphane
by this nano-catalyst. Various parameters such as solvent type,
surface groups into phosphane oxide using H2 O2 . The structure
oxidant type and recyclability were examined in order to find the
of HM-Mo catalyst was fully characterized by TEM, XRD, 29 Si CP
optimum reaction conditions. The use different solvents proved MAS NMR, 13 C CP MAS NMR and 31 P CP MAS spectra. For com-
that magnetic MoO2 NPs showed excellent performance for epox- parison, the complex [MoCl2 (O)2 (OP(CH2 CH3 )(Ph)2 )2 ](1) was also
idation reaction in carbon tetrachloride (CCl4 ). Among various synthesized by the reaction of [Mo(O)2 Cl2 ] with the phosphane
oxidants, tert-butyl peroxide (tBuOOH) was selected as the oxidant oxide ligand CH3 CH2 (Ph)2 PO. Catalytic experimental showed that
for epoxidation reactions. Catalytic reusability of as-prepared cat- both catalysts had almost similar performances in the epoxidation
alyst was tested in the epoxidation of cis-cyclooctene for six runs. of cis-cyclooctene, 1-Octene and trans-2-Octene in the presence
Experimental results showed a 5% decrease in the yield of epoxide of tBuOOH at 55 ◦ C. When limonene with two different double
product which was 99% in the first run. In addition, this reaction bonds was used as substrate, the best regioselectivity was achieved
was carried out under the same condition by as-synthesized cata- by HM-Mo as catalyst with 90% conversion for the corresponding
lyst with two different silica coating, namely dense silica and dense epoxide. In comparison with complex (1), this high regioselectivity
silica/mesoporous silica in order to evaluate the effect of silica layer can be attributed to the uniform, single site and nanostructure of
on the catalytic performance of magnetic MoO2 NPs. When the HM-Mo catalyst.
 A. Akbari et al. / Nano-Structures & Nano-Objects 14 (2018) 19–48
Fig. 14. The catalytic redox cycle according to the Mars–van Krevelen reaction mechanism [100].
Unlike Ni-based catalysts, Molybdenum dioxide NPs can be
used as new catalytic materials in the process of Jet-A fuel [97–
99] directly due to their unique properties such as high oxidation
activity toward Jet-A fuel, high resistance to coking, stability at
high operating temperatures and high sulfur tolerance. In this way,
MoO2 NPs with uniform structures were prepared using molybde-
num trioxide as the starting material in a mixture of ethylene glycol
and water at 180 ◦ C for 12 h [100]. Catalytic activity of as-prepared
MoO2 NPs was tested for partial oxidation of liquid hydrocar-
bons such as n-dodecane at 850 ◦ C and 1 atm. For comparison,
the same oxidation reaction with similar conditions was carried
out by Ni-based catalysts and commercial MoO2 . Experimental
results revealed that MoO2 NPs not only had significantly higher
fuel conversion of >90% with a hydrogen yield of >70% but also
showed a remarkable coking resistance. In contrast, the catalytic
performance of Ni-based catalysts and commercial MoO2 was low
due to their low coking resistance which led to deactivation of
their surfaces. Moreover, the mechanism of partial oxidation of n-
dodecane could be explained based on the Mars–van Krevelen re-
action mechanism. The catalytic redox cycle is depicted in Fig. 14.
In this mechanism, adsorption of hydrocarbons occurred on the
surface of metal oxide NPs, followed by oxidation of the adsorbed
hydrocarbons. Next the insertion of oxygen atoms occurred by re-
duction of the metal oxide. This cycle was repeated by re-oxidation
of the metal oxide surface, followed by refilling surface oxygen
vacancies by gas-phase oxygen.
The activity, selectivity and stability of heterogeneous cata-
lysts are affected by many factors such as preparation method,
the catalyst precursor, reaction temperature and solvents. Among
them, transition metal oxide precursor is an important factor,
so the choice of appropriate transition metal precursor can sig-
nificantly affect the catalyst properties. For example, Arnold and
coworkers [101] synthesized metallosilicates containing molyb-
denum using two different starting materials, namely Mo(OiPr)5
and MoO2 (acac)2 in the presence of tetraethoxysilane (TEOS) by
sol–gel process [102]. The catalytic activity of these catalysts was
evaluated for epoxidation of cyclooctene in the presence of TBHP
as a green oxidant. The results demonstrated that the prepared-
catalyst using MoO2 (acac)2 as starting material showed high con-
version (94%) and selectivity (97%) toward the epoxide product.
In the case of Mo(OiPr)5 as precursor, 82% conversion with 95%
selectivity was achieved. Further, the general scope of these cat-
alysts was tested for epoxidation of various olefins and showed
reusability for three times. However, catalysts showed leaching of
the active species in subsequent runs which limited their applica-
tion as catalyst.
Supported metal NPs can be utilized in the structure of catalysts
in order to prevent leaching of the active species. For instance, a
reverse micelle microemulsion method was developed for the syn-
thesis of very small MoO3 NPs [103]. By this method, as-prepared
MoO3 NPs (1.5–4 nm) were uniformly dispersed and supported
onto SiO2 (MoO3 /SiO2 , ∼275 nm), TiO2 (MoO3 /TiO2 , ∼10.5 nm)
29
and ZrO2 (MoO3 /ZrO2 , ∼6.5 nm) nanospheres. The stability of the
alkoxide precursors of silica, titania and zirconia can be related
to the differences in particle size. On the other hand, tetraethyl
orthosilicate (TEOS), as silica precursor, was more stable than
titanium (IV) butoxide and zirconium (IV) butoxide, as precursor of
titania and zirconia, respectively. The stability of TEOS decreased
the rate of hydrolysis, nucleation as well as the crystal growth,
resulting in the formation of larger particles in the range of 250–
300 nm. These hybrid catalysts were fully characterized by various
physico-chemical techniques. In order to optimize the oxidation
reaction conditions, catalytic activity of the hybrid catalysts was
evaluated for the epoxidation of cyclooctene in the presence of
TBHP as an oxidant. The experimental results at the optimized
condition (T = 80 ◦ C, solvent: 1,2-dichloroethane and t = 2 h)
showed that MoO3 /SiO2 catalyst gave 90% cyclooctene conversion
and 100% selectivity for epoxide product. However, MoO3 /TiO2
and MoO3 /ZrO2 showed the same selectivity but their cyclooctene
conversion were 37% and 39.5%, respectively. In addition, the scope
of the substrate by choosing other alkenes as well as the leaching
experiment was carried out using MoO3 /SiO2 as the best catalyst.
This catalyst did not show any loss of catalytic activity or leaching
even after five runs.
Generally, olefins with electron-donating groups are more ac-
tive than olefins with electron-withdrawing groups in epoxidation
reactions [104]. For instance, the epoxidation of allyl acetate, as a
low active substrate, was carried out by supported MoO3 particles
over SiO2 , TiO2 and Al2 O3 in the presence of TBHP as an oxi-
dant [105]. In this research, MoO3 particles supported on Al2 O3 and
SiO2 were ineffective for epoxidation of allyl acetate. In the case of
MoO3 particles supported on TiO2 , excellent catalytic performance
in epoxide selectivity was achieved which could be related to the
high surface of TiO2 as well as the two-dimensional dispersion of
MoO3 . It is worth to highlight that epoxidation of allyl acetate with
MoO3 supported on TiO2 in the presence of TBHP was significantly
temperature dependent.
As mentioned before, epoxidation of allyl acetate over
MoO3 /Al2 O3 produced a small amount of glycidyl acetate as the
epoxy product. This very low yield can be attributed to the ex-
istence of acid sites in the structure of MoO3 /Al2 O3 which easily
cleaved the epoxy ring of glycidyl acetate during the reaction.
In one study, various types of amines such as pyridine, pyridine
derivatives and aliphatic amines were utilized during the reaction
to neutralize the acid sites [106]. Among them, pyridine and pyri-
dine derivatives showed high selectivity for the epoxidation of allyl
acetate toward glycidyl acetate. These amines not only activated
MoO3 /Al2 O3 catalyst by coordinating to Mo but also blocked acid
sites and inhibited the ring-opening of glycidyl acetate.
In another reported research, the effect of amine additives
(pyridine and pyrazole) was comprehensively investigated for the
epoxidation of simple olefins such as styrene and cyclohexene by
MoO3 particles as catalyst [107]. Preliminary results revealed that
the epoxidation of styrene by MoO3 particles as catalyst strongly
30 A. Akbari et al. / Nano-Structures & Nano-Objects 14 (2018) 19–48
depended on the amount of amine loading. For example, the olefin
conversion dropped from 88% to 76% and 68% by increasing the
pyrazole from 0.17 to 0.15 and 0.5 mol%, respectively. In the case
of pyridine, the same situation was observed. It seems that the
high concentration of amines improved the activity of Mo (VI)
species which caused the oxidative cleavage of the epoxide instead
of protecting the oxirane ring. Gao and coworkers utilized one-
dimensional (1D) molybdenum oxide nanowires as a precur-
sor for preparation of organic–inorganic materials (Fe–MoOx /PANI
nanorods) in the presence of aniline and Fe3+ [108]. In this pro-
cedure, Mo3 O10 (C6 H5 NH3 )2 ·2H2 O NWs was used as precursor and
reacted with Fe3+ for 2 h. After the addition of aniline, Fe3+
ions acted as initiator and polymerized aniline on the surface of
Mo3 O10 (C6 H5 NH3 )2 ·2H2 O NWs. It is worth to mention that using
Mo3 O10 (C6 H5 NH3 )2 ·2H2 O NWs as starting material was vital for
the preparation of Fe–MoOx /PANI nanorods because the surface
of Mo3 O10 (C6 H5 NH3 )2 ·2H2 O NWs facilitated material dissolution
and aniline polymerization. Different precursors with various mor-
phologies such as Mo7 O24 (NH4 )6 ·4H2 O, Mo8 O26 (C6 H5 NH3 )4 ·2H2 O
in bulk form and Mo6 O19 (C6 H5 NH3 )2 needles were used in produc-
ing Fe–MoOx /PANI nanostructures. Moreover, the catalytic behav-
ior of these MoOx -based hybrid catalysts was evaluated for epox-
idation of cyclooctene as a probe reaction. Experimental results
showed that Fe–MoOx /PANI nanorods acted as efficient catalysts
with 98.8% olefin conversion and 97.2% selectivity toward the
formation of epoxide product. Fe–MoOx/PANI nanorods can be
recycled and reused for more than 5 runs without significant loss
in their catalytic activity. In contrast, MoOx/PANI nanorods were
deactivated after 2 runs. Therefore, it could be concluded that Fe3+
ions improved stability of the catalyst via formation of insoluble
ferric molybdate [109].
Recently, an efficient magnetic γ -Fe2 O3 @C@MoO3 based cata-
lyst with core–shell structure was produced and used for epox-
idation of cyclooctene with tBuOOH as an oxidant [110]. In this
method, glucose as the carbon source was used for the coating
of magnetic NPs which prevented their aggregation and stabilized
the NPs. Modification of as-prepared material with poly (dial-
lyldimethylammonium chloride) (PDDA) facilitated the adsorption
of Mo7 O624− ions on the surface of magnetic microspheres. Finally,
multifunctional hybrid material, γ -Fe2 O3 @C@MoO3 , was obtained
by a hydrothermal process at 180 ◦ C for 16 h. The catalytic func-
tion of as-prepared material showed 100% conversion and 99%
selectivity toward the formation of epoxide product. In addition,
the catalyst showed high catalytic performance even after 9 runs
with 94.7% conversion and 99.6% selectivity. Fig. 15 illustrates the
reaction mechanism of epoxidation which is based on the FT-IR and
XPS measurements.
This mechanism suggests that two transition states, namely
olefin complex and Mo-alkyl peroxide, were substantial for the
high activity of catalyst.
2.3.2. Tungsten oxide nanoparticles
It is well established that immobilization of well-dispersed
nanoscopic materials in high-surface area supports can enhance
their catalytic activity as well as product selectivity. In this regard,
tungsten oxide NPs were immobilized on various supports such
as SBA-15, MCM-48 and MCF and then used in a wide variety of
oxidation reactions.
For instance, tungsten (VI) oxide NPs were uniformly dispersed
on the surface of an ordered mesoporous support (MCM-48) [111].
The as-prepared WO3 -MCM-48 (2–3 nm) catalyst was utilized
as an outstanding heterogeneous catalyst for the oxidation of
different substrates such as sulfides, olefins and cyclic ketones
in the presence of peracetic acid or hydrogen peroxide. In the
aforementioned research, the influence of the nature of supporting
materials and their size were evaluated by using different kind of
supports in the epoxidation of cis-cyclooctene as a probe reaction
in the presence of 50% aqueous H2 O2 . Results revealed that the
epoxidation efficiency was dramatically decreased by employing
MgO and Montmorillonite K10, whereas the use of TiO2 , CeO2 ,
active carbon, or alumina produced moderate activities. In con-
trast, MCM-48 as a support for WO3 resulted in 98% conversion
and selectivity. The catalytic activity of WO3 -MCM-48 (2–3 nm)
was also tested in the oxidation of a broad range of substituted
sulfides. It is worth mentioning that the sulfide oxidation by WO3 -
MCM-48 (2–3 nm) was significantly dependent on the reaction
conditions. On the other hand, complete conversion of sulfoxides,
produced using 1.1 equiv of aqueous H2 O2 (50%) for 4 h at 25 ◦ C
in methanol, to sulfones occurred in the presence of 3.0 equiv of
aqueous H2 O2 (50%) at 60 ◦ C for 12 h. In addition, WO3 -MCM-
48 (2–3 nm) catalyzed the oxidation of ketones to lactones, the
Baeyer–Villiger oxidation, with periodic acid in acetonitrile at 60 ◦ C
for 12 h.
SBA-15 was utilized as another mesoporous silica support in
the preparation of tungsten oxide based nanocomposites. In one
research, atomic layer deposition (ALD) method was reported for
grafting tungsten oxide species onto mesoporous silica (SBA-15)
surfaces [112]. Well dispersion of tungsten oxide NPs on the sur-
face of SBA-15 and improvement in thermal stability were the main
advantageous of atomic layer deposition (ALD) method. The as-
prepared WOx -SBA-15 was used as catalyst in the dehydration of
2-butanol and methanol. Experimental results showed that this
catalyst exhibited excellent activity compared to WOx -SBA-15 pre-
pared by conventional methods.
WO3 /SBA-15(OA), WO3 /SBA-15(HP) and WO3 /SBA-15(AM)
were synthesized by dissolving tungstic acid, WO3 · H2 O, in aque-
ous solution of oxalic acid, hydrogen peroxide and ammonium
paratungstate, respectively, using the conventional incipient wet-
ness impregnation method [113]. The catalytic performance of as-
prepared nanomaterials was studied for selective oxidation of cy-
clopentene (CPE) to glutaraldehyde (GA). The dispersion or aggre-
gation of tungsten oxide NPs onto the supports were analyzed by
transmission electron microscopy (TEM) and X-ray powder diffrac-
tion (XRD). According to these analyses, the dispersion of tungsten
species obeyed the order WO3 /SBA-15(OA) > WO3 /SBA-15(HP) >
WO3 /SBA 15(AM). It is worth highlighting that the title reaction
was carried out with the same order. On the other hand, WO3 /SBA-
15(OA) and WO3 /SBA-15(HP) catalysts exhibited perfect catalytic
behavior as compared with WO3 /SBA-15(AM) and homogeneous
tungstic acid catalysts for the title reaction not only in terms of
conversion of CPE but also in terms of selectivity toward GA.
In another report, an efficient and stable WOx -SBA-15 nano-
composite catalyst was obtained using the hydrothermal method
[114]. In this protocol, tetraethylorthosilicate (TEOS), aqueous
sodium tungstate solution (NaWO4 ·2H2 O, 0.5 M) and a polyethy-
lene oxide-block-polypropylene oxide-block-polyethylene oxide
triblock copolymer were used as silica source, tungsten source
and structure-directing agent, respectively. This nanocomposite
catalyst showed high activity in selective oxidation of sulfides to
sulfoxides in the presence of 70% aq. tert-butyl hydrogen peroxide
at room temperature. In the selective oxidation of allyl phenyl
sulfide to corresponding sulfoxides, experimental results demon-
strated that overoxidation to the sulfone or epoxidation of the
double bond did not occur. Successful oxidation of various sulfur
compounds with high selectivity and conversion over this catalyst
could be related to the large pore diameter and low surface acidity
of WOx -SBA-15.
Nano-supported tungsten oxide SBA-15 materials have lim-
itations such as low thermal stability, structure collapse after
high-temperature calcinations, and inherent leaching. In order to
overcome these obstacles, mesocellular silica foams (MCF) were
prepared and used as a new support in the preparation of sup-
ported tungsten oxide NPs [115]. In this work, WO3 -MCF catalyst
 A. Akbari et al. / Nano-Structures & Nano-Objects 14 (2018) 19–48
Fig. 15. Possible epoxidation reaction mechanism [110].
Fig. 16. Possible main-product and by-products of epoxidation of cycloocta-1,5-diene [115].
was synthesized by adding sodium tungstate (Na2 WO4 ·2H2 O, 0.2
M) aqueous solution to the mixture of Pluronic P123 triblock
polymer, 1,3,5-trimethylbenzene and Si(OC2 H5 )4 (TEOS), followed
by calcination at 500 ◦ C in air for 8 h [116]. After calcination,
as-prepared material was treated by ammonium acetate (AMA)
to rapidly balance the percentage of tungsten between the solu-
tion and catalyst. The catalytic activity of these materials were
evaluated for the epoxidation of cycloocta-1,5-diene (COD) and
their performances were compared with other mesoporous silica
supported tungsten oxide catalysts (WO3 -SBA-15 and WO3 -MCM-
41). Characterization of the materials demonstrated the formation
of ultra-large pores and unique 3-D cell-window structure (18–
24 nm) in WO3 -MCF material. Moreover, AMA treatment removed
loosely bonded tungsten species from WO3 -MCF surface. With this
treatment, only single-site tetrahedra (WO4 ) species remained on
the surface which enhanced the catalytic activity of WO3 -MCF. The
oxidation reaction of COD is depicted in Fig. 16 showing the main-
product and by-products.
The effect of different parameters such as the type of support,
tungsten oxide loading, AMA-treatment cycles, calcination tem-
perature as well as the reaction time were fully investigated for
the epoxidation of COD in the presence of H2 O2 . All experimental
results demonstrated that the catalytic activity of WO3 -MCF mate-
rials for the title reaction was higher than WO3 -SBA-15 and WO3 -
MCM-41.
In 2011, Kamata and coworkers reported new catalysts based
on the combination of tungsten with various metals (W–X/SnO2 , X
= Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Y, La, Ce, Pr, Sm, Eu, Dy, Yb, Ni,
31
Cu, Ag, Zn, Cd, Ga, and In) as additives which were supported on
SnO2 [117]. The catalytic performance of W–X/SnO2 significantly
depended on the additives (X). As a probe reaction, the epoxidation
of 1-hexene was studied over W–X/SnO2 catalyst in the presence
of 60% aqueous H2 O2 . Results showed that the highest yield (93%)
with a 95% selectivity for 1,2-epoxyhexane could be obtained over
W–Zn/SnO2 . In contrast, when X was from groups 10–14 elements,
catalyst activity was moderate and when X was from groups 1–
3, the catalyst was not active. Dimethyl carbonate (DMC) was
selected as the best solvent for the title reaction. The catalytic
activity of W–Zn/SnO2 system for the oxidation of various amines,
silanes, sulfides and alkenes into the corresponding N-oxides,
silanols, sulfoxides and epoxides was evaluated in the presence of
H2 O2 as a green oxidant. Experimental results demonstrated that
polytungstates with dioxo groups in W–Zn/SnO2 had a critical role
in the oxidation process.
2.4. Group 7 elements (Mn, Tc and Re)
2.4.1. Manganese oxide nanoparticles
2.4.1.1. Alcohol oxidation. Recently, extensive research has been
devoted to aerobic oxidation of alcohols by manganese oxide NPs.
These studies showed significant catalytic activity and selectivity
even up to 100% [118]. In general, catalytic performance of the NPs
depended on particle size. On the other hand, smaller particle sizes
led to higher activity in oxidation reactions. In contrast, NPs were
not stable and prone to aggregate formation with decreasing par-
ticle size which reduced their stability and catalytic activity [119].
32 A. Akbari et al. / Nano-Structures & Nano-Objects 14 (2018) 19–48
Fig. 17. Illustration of general pathway for MnO2 /GO nanocomposite synthesis and its application in the oxidation of benzyl alcohol [120].
This problem could be solved by immobilization of active species
onto solid supports. For instance, Xiang and coworkers developed
a new route by decoration of MnO2 NPs on Graphene oxide. In
this work, MnO2 /GO composites exhibited a high performance in
the oxidation of benzyl alcohol to benzaldehyde in the presence
of air as an oxidant [120]. Overall schematic representation of this
protocol is depicted in Fig. 17.
As shown in Fig. 17, MnO2 /GO composite was synthesized by a
simple in-situ growth method using MnSO4 and GO as the source of
Mn ions and support, respectively. Well dispersed ultrafine MnO2
NPs (ca. 3 nm) could be synthesized by the simple in-situ growth.
The key point is the combination of GO with MnO2 which has a syn-
ergistic effect on catalytic activity of MnO2 /GO composites. 96.8%
benzyl alcohol conversion and 100% benzaldehyde selectivity was
obtained over MnO2 /GO (10/100) catalyst within 3 h under 383 K.
Our research group prepared MnO2 NPs via a simple and
novel protocol and used for the oxidation of benzylic alcohols
to corresponding aldehydes [121]. In our approach, MnO2 NPs
were obtained in-situ by the reaction of Mn (II) (tptz)-Cl2 (H2 O)
as a mononuclear complex with oxone where tptz and oxone
are 2,4,6-tris(2-pyridyl)-1,3,5-triazine ligand and 2KHSO5 ·KHSO4 ·
K2 SO4 oxidant, respectively. EPR spectroscopy enabled us to pro-
pose a mechanism for the formation of MnO2 NPs from Mn (II)
(tptz)-Cl2 (H2 O). Based on experimental results, we concluded that
III,IV
the accumulation of mononuclear complexes such as Mn2 oc-
curred before the formation of MnO2 NPs. Existence of the ligand
around Mn oxide particles not only played an important role in the
formation of NPs but also increased the activity and selectivity of
MnO2 NPs toward alcohol oxidation.
In another work, we synthesized nanolayered Mn oxides in the
presence of CaCl2 ·4H2 O and used them as catalysts for alcohol
oxidation under ambient condition [122]. High surface area, ther-
modynamic stability, and low surface enthalpy are some of the
advantages of these layered structures. Catalytic performance of
Ca0.16 MnO2 ·2H2 O was examined in the oxidation of benzyl alcohol
as a model reaction. Different oxidants such as TBHP, H2 O2 , NaClO
and molecular oxygen with various solvents were tested at room
temperature. 100% conversion and 85% selectivity were obtained
in acetonitrile and in the presence of O2 as an oxidant.
Recently, several promoters with synergistic effects have been
developed to increase the catalytic activity of MnOx systems in
the oxidation of benzyl alcohol. For example, in one report, Ce and
Fe were added on the structure of MnOx materials and the redox
properties as well as the reactivity of MnOx system as a catalyst in
liquid phase were rigorously studied for the selective oxidation of
benzyl alcohol [123].
Aerobic oxidation of 5-Hydroxymethylfurfural (HMF) to 2,5-
diformylfuran (DFF) is one of the most important reactions in or-
ganic transformations. DFF is known as a versatile intermediate for
the synthesis of many important products. Selective oxidation of
HMF to DFF is difficult because of the existence of the more reactive
α, β -unsaturated aldehyde group in HMF. In this regard, different
catalytic systems have been tested for selective oxidation of HMF
to DFF. Liu and coworker used a cryptomelane-type manganese
oxide octahedral molecular sieve with a (2 × 2, 4.6 Å × 4.6 Å) tunnel
size (OMS-2) in order to catalyze the oxidation of HMF to DFF with
a high yield of 97.2% at 383 K and 0.5 MPa O2 in DMF [124]. In
this study, catalytic activity of other MnO2 catalysts with different
structures and morphologies were also tested. Results showed that
OMS-2 has high activity and selectivity due to its tunnel structure
as well as its ability for reduction and oxidation.
Versatility of OMS-2 as a green and efficient catalyst was
demonstrated by the oxidative amidation of primary alcohols or
aldehydes to primary amides in aqueous ammonia. In one com-
prehensive study, Mizuno and colleagues utilized OMS-2 and other
manganese-based catalysts with different structures to oxidize
various kinds of structurally diverse primary alcohols or aldehy-
des into the corresponding primary amides in moderate to high
yields [125]. A four-step mechanism was proposed for the OMS-2-
catalyzed amidation. As shown in Fig. 18, the steps include: (i) aer-
obic oxidative dehydrogenation of primary alcohols to aldehydes
(step 1), (ii) dehydrative condensation of the aldehydes and ammo-
nia to aldimines via hemiaminal intermediates (step 2), (iii) aerobic
 A. Akbari et al. / Nano-Structures & Nano-Objects 14 (2018) 19–48
Fig. 18. Four-step route toOMS-2-catalyzed amidation of primary alcohols to primary amides [125].
oxidative dehydrogenation of the aldimines to nitriles (step 3),
and (iv) successive hydration to the corresponding primary amides
(step 4).
Ghosh and coworkers devised an innovative approach to syn-
thesize Mn2 O3 with rod-shape nanostructures [126]. In this simple
method, the mixture of polyethylene glycol (PEG) and sodium
dodecyl sulfate (SDS) were used as a soft template for Mn2 O3 pro-
duction from Mn(OAc)2 ·4H2 O as the precursor. The as-prepared
Mn2 O3 nanorods exhibited enhanced catalytic performance for
direct synthesis of various important aldehydes via oxidation of
alcohols with high chemoselectivity.
2.4.1.2. Epoxidation. Manganese oxide NPs are recognized as effi-
cient catalysts in the oxidation of olefins. Epoxides, as products, are
found in many important intermediates as well as pharmaceutical
materials [127,128].
Recently, we developed a simple, safe and economical method
to prepare nano-sized particles of manganese oxide by decompo-
sition of an aqueous solution of manganese nitrate at 100 ◦ C [129].
The synthesized metal oxide NPs were characterized using FT-IR,
SEM, TEM and XRD. We also investigated the catalytic performance
of manganese oxide NPs in epoxidation of various olefins in the
presence of H2 O2 . Results showed that the nano-catalyst has ex-
cellent activity toward epoxidation of aromatic olefins but mild
activity for epoxidation of non-aromatic olefins. Reusability of the
catalyst was also tested which was 86% conversion after six runs.
The proposed mechanism for epoxidation of olefins by manganese
oxide NPs is schematically depicted in Fig. 19.
We have synthesized nano-layered manganese oxides which
are embedded in calcium (II), zinc (II) or aluminum (III) and used
as a catalytic system for epoxidation of various olefins using anhy-
drous tert-butyl hydroperoxide (TBHP) as the oxidation reagent.
The production of these metal oxide NPs can be easily scaled up
via simple, cheap and environmentally friendly processes without
using any toxic organic materials [130].
33
Fig. 19. Presentation of proposed mechanism for olefin epoxidation over man-
ganese oxide [129].
Four different kind of manganese oxides (MnO, MnO2 , Mn2 O3
and Mn3 O4 ) were synthesized via solid-state reaction procedures
and used as a catalytic system in epoxidation of various olefins
in the presence of 30% H2 O2 as an oxidant in bicarbonate solu-
tion [131]. Comparison of catalytic activity of these manganese
oxides revealed that MnO has superior activity for the conversion
of styrene to obtain 92.4% selectivity of the corresponding epoxide.
Furthermore, these findings confirmed that manganese must be
in its lowest oxidation state, implying that the oxidation state
of manganese has a substantial role in determining the catalytic
activity of the manganese oxide species. In addition, bicarbonate
solution has a critical role in epoxidation because no product was
obtained in the absence of bicarbonate solution. According to the
proposed reaction mechanism in Fig. 20, the nucleophilicity of
HCO− 4 ions are more than H2 O2 and subsequently act as an efficient
oxidant in this system.
In this mechanism, coordination of HCO− 2+
4 with Mn on the
surface of catalyst can produce intermediate (I). This intermediate
possesses active atomic [O] which can be transferred to the C–
C bond of alkene molecule, forming the epoxide product. Mn2+
is produced by quick decomposition of intermediate (II) on the
surface of catalyst.
34 A. Akbari et al. / Nano-Structures & Nano-Objects 14 (2018) 19–48

Fig. 20. Proposed mechanism for epoxidation of olefins over manganese oxide [131].

Two different types of manganese oxide NPs, Mn2 O3 and

Mn3 O4 , were synthesized via a solid-state thermal decomposition
of manganese terephthalate metal–organic framework (MOFs) as
a precursor [132]. In this procedure, Mn2 O3 NPs were obtained
as a black powder at 600 ◦ C after 6 h and Mn3 O4 NPs as a fine
brown powder at 500 ◦ C after 4 h using [Mn3 (BDC)3 (DMF)4 ]n as
the starting material. In this study, the oxidation of cyclohexene or
styrene by Mn3 O4 NPs was chosen as a model reaction in order to
investigate the reaction conditions as well as the catalytic mecha-
nism. Optimized reaction conditions were achieved in the presence
of TBHP in acetonitrile at 75 ◦ C for 7 h. Oxidation mechanism was
studied in detail by adding ionol (2,6-di-tertbutyl-p-cresol) as a
radical scavenger. As a result, the oxidation reaction was stopped
in the presence of ionol which demonstrated the formation of
epoxides via a dominant radical pathway.
The Sono-chemical process as a simple and green method has
been used extensively for preparation of nanomaterials [133,134].
For instance, uniform sphere-like Mn3 O4 nanocrystals were ultra- Fig. 21. TEM images of Au and Ag deposited on layered manganese oxides.
sonically synthesized by the reaction of Mn(OAc)2 as precursor Source: Reproduced from Ref. [138] with permission from The Royal Society
with tetramethylammonium hydroxide (TMAH) in a mixture of of Chemistry.
water and ethanol as solvents [135]. The catalytic activity of these
NPs was compared with bulk catalyst. Findings showed that the
epoxidation of styrene and cyclooctene can be carried out in the Mn oxides causes 10–30% improvement in epoxidation compared
presence of Mn3 O4 nanocrystals in short reaction times and rather to other Mn oxides. According to previous mechanisms for the
low temperatures with 100 and 92% conversion for styrene and epoxidation reaction and as shown in Fig. 22, electron exchange
cyclooctene, respectively. occurred between Au or Ag and Mn ions [139–141]. We assumed
Recently, Au and Ag were utilized as electronegative transition that the coordination of HCO−
4 ions on the surface of Mn ions made
metals for conversion of low valence metal ions to high valence be- an intermediate which facilitated the transformation of active
cause high valence metal ions take part in most oxidation reactions. oxygen atom to the olefin to produce the epoxide.
This fact was reported by other research groups as well [136,137]. 2.4.1.3. Miscellaneous oxidation reactions. For the first time,
In this regard, our research group developed a new catalytic system Suib and coworkers prepared γ -MnO2 octahedral molecular
by deposition of Au and Ag on layered Mn oxides using a very sieves [142]. They used this system as a catalyst for solvent-free
simple method [138]. It is worth to mention that the best catalytic oxidation of toluene in an atmospheric reflux safe system with
activity was achieved when the amount of Au and Ag were less than molecular oxygen. Experimental results showed a 47% conversion
4%, which is suitable from an economical viewpoint. Deposition of of toluene, 57% selectivity toward benzoic acid and 15% for ben-
these metals on the surface of Mn oxides could be easily observed zaldehyde.
from TEM images as separated islands (Fig. 21). Formaldehyde removal by oxidation reaction is one of the most
We have tested the oxidation activity of these catalysts for important environmentally-friendly processes due to its harm-
epoxidation of some olefins. Our experimental results showed that ful effects on eye, nose, nervous system and cardiovascular sys-
the existence of Au and Ag in the range of 0.5–2% in the structure of tem [143]. Mn oxides can be used as catalyst in this process
 A. Akbari et al. / Nano-Structures & Nano-Objects 14 (2018) 19–48
Fig. 22. Proposed mechanism for epoxidation of alkenes over Au–Mn or Ag–Mn oxides [138].
because the catalytic activity of Mn oxides can be easily tuned
by the preparation method, their morphology and tunnel struc-
tures [144,145]. In one report, α -, β -, γ - and δ -MnO2 with different
crystal structures were synthesized by hydrothermal method and
used as catalysts for oxidation of formaldehyde [146]. Experimen-
tal results showed that δ -MnO2 had the best catalytic activity with
100% formaldehyde conversion at 80 ◦ C compared to other Mn
oxides. High catalytic activity of δ -MnO2 originated from its special
2D layer tunnel structure as well as the highest content of lattice
oxygen species on the catalyst surface.
Solvent-free aerobic oxidation of hydrocarbons was carried out
in the presence of Mn3 O4 NPs [147]. These NPs were successfully
synthesized via a facile one-pot etherification at low temperature.
Controlling the size of the synthesized Mn3 O4 NPs by changing the
reaction temperature was the key point of this study. On the other
hand, when the reaction temperature was 90 and 120 ◦ C, uniform
and well-dispersed Mn3 O4 NPs with average size of 10 nm was
obtained. By increasing the reaction temperature to 150 ◦ C, the NP
size increased to an average size of 15 nm. In order to investigate
the catalytic capability of as-prepared Mn3 O4 NPs, oxidation of
ethylbenzene was selected as a model reaction. Compared to other
catalysts such as commercial Mn3 O4 and manganese acetate, the
as-prepared Mn3 O4 NPs showed 50% conversion and 81% ace-
tophenone selectivity in solvent-free condition at 130 ◦ C for 8 h.
2.5. Group 8 elements (Fe, Ru and Os)
2.5.1. Iron oxide nanoparticles
In recent years, considerable effort has been devoted to the
preparation and application of iron oxide NPs due to their unique
properties such as low toxicity, good dispersibility, and easy sep-
aration using an external magnetite. Compared to other transition
metal oxides as catalysts and from the view point of catalytic
application, magnetic recoverability can be a unique advantage
which eliminates catalyst separation by centrifugation or filtration
after completion of the reaction. In most cases, iron oxide NPs
are shielded by capping agents, especially silica based agents, to
35
prevent their aggregation as well as for ease of post-modification.
The application of ‘‘free’’ iron oxide NPs as a catalyst is rare.
In one report, bulk α -F2 O3 , bulk γ -F2 O3 , nano-γ -F2 O3 (particle
size of 20–50 nm) and nano-γ -F2 O3 (particles size of 3–5 nm)
were utilized in the oxidation of various alcohols and olefins to
corresponding carbonyl products [148]. The efficiency of these
catalysts was studied in selective oxidation of benzyl alcohol as a
probe molecule in the presence of 33% H2 O2 at 75 ◦ C. The particle
size of as-used iron oxide NPs had a substantial effect on conver-
sion and selectivity of benzyl alcohol oxidation. The conversion
and selectivity increased in the order of nano-γ -F2 O3 (3–5 nm)
>nano-γ -F2 O3 (20–50 nm) > bulk α -F2 O3 >bulk γ -F2 O3 . The high-
est catalytic activity belonged to nano-γ -F2 O3 (3–5 nm) with 85%
conversion and 35% selectivity. Furthermore, unsupported ‘‘free’’
nano-γ -F2 O3 was used as an efficient catalyst in the oxidation of
styrene and its derivatives to aldehydes using H2 O2 as a green
oxidant. The use of ‘‘free’’ nano-F2 O3 in place of immobilized nano-
F2 O3 was the significance of these results.
Ultrasound-activated reaction was employed by Askarinejad
and colleagues for the synthesis of α -F2 O3 (hematite) NPs [149].
In this method, the uniform and crystalline α -F2 O3 (hematite) NPs
were synthesized via ultrasound irradiation of Fe(OAc)2 alkaline
solution followed by calcination at 900 ◦ C, as shown in Fig. 23.
The catalytic activity of nano-sized α -Fe2 O3 and α -Fe2 O3 in bulk
catalysts were examined in the oxidation of methyl phenyl sulfide
as a probe reaction. After evaluation of many parameters, 0.01
mmol of catalyst and 0.4 mmol ultrahigh-pressure (UHP) for 1 h at
50 ◦ C were selected as the optimum reaction conditions. For nano-
sized α -Fe2 O3 , 95% conversion of methyl phenyl sulfide and 88%
selectivity toward sulfoxide were obtained while α -Fe2 O3 in bulk
gave 54% conversion for this reaction. These results indicated that
size had a remarkable influence on catalytic performances.
Recently, ferric hydroxide, Fe(OH)3 , was prepared by a homo-
geneous chemical precipitation method and utilized as a precursor
in the preparation of α -F2 O3 (hematite) NPs by calcination in the
presence of polyethylene glycol of different molecular weights
(PEG 400 and PEG 4000) [150]. The key advantage of this method
36 A. Akbari et al. / Nano-Structures & Nano-Objects 14 (2018) 19–48
Fig. 23. Preparation method for hematite nanoparticles [149].
was the use of PEG as a surfactant which had a direct influence on
particle size as well as size distribution of as-prepared catalysts.
TEM results demonstrated that the size of α -F2 O3 (hematite) NPs
was around 5–20 nm and 10–50 nm in the presence of PEG 400 and
PEG 4000 as surfactants, respectively. Furthermore, the size of α -
F2 O3 (hematite) NPs was approximately 50–100 nm in the absence
of surfactant. The catalytic potential of as-prepared catalysts was
evaluated in the oxidation of benzyl alcohol and its derivatives in
the presence of periodic acid as an oxidant. Experimental results
showed that highest conversion and selectivity were obtained in
the presence of PEG 4000 modified nano α -Fe2 O3 in which the NPs
were well dispersed and had the smallest size.
Das and coworkers developed a new and facile method based on
polyvinyl alcohol (PVA) as a biocompatible and nontoxic polymer
to prevent agglomeration of iron oxide magnetic NPs [151]. As
demonstrated previously, uniform and mono-dispersed particles
are very important for the performance of iron oxide based cat-
alysts. In this method, first an aqueous solution of iron (III) was
mixed and dispersed in PVA solution in alkaline media. Next, the
brown gel was dried in an open beaker in a water bath at 85 ◦ C.
Finally, two types of magnetic iron oxide NPs were obtained by
thermolyzing a PVA–Fe(OH)3 gel matrix at 400, 500, 600, and
700 ◦ C. The calcination temperature of PVA based gels had a
significant effect on the nature of iron oxide magnetic products.
Heating the gel at 700 ◦ C resulted in the formation of α -F2 O3 NPs
whereas heating the gel to 400, 500, 600 ◦ C lead to the formation
of γ -F2 O3 NPs as the sole product. Selective epoxidation of styrene
was carried out in the presence of α -F2 O3 NPs in aqueous solution
of TBHP as the oxidant. Experimental results showed that styrene
conversion and selectivity increased by increasing the reaction
time. After 6 h of reaction, reaction conversion and selectivity for
epoxide reached 73% and 77%, respectively.
Different types of mesoporous silica materials can be used
as a support for stabilization of metal NPs. Among them, SBA-
15 has gained significant attention due to its high surface area,
thermal stability, and large pore diameter. Highly active F2 O3
NPs embedded in SBA-15 were synthesized by the hydrothermal
method [152]. As shown in Fig. 24, the as-prepared Fe2 O3 /SBA-15
showed excellent catalytic performance in oxidation of alcohols
and sulfides.
In this study, the effect of many factors such as catalyst loading,
reaction temperature, type of oxidant, solvent and the reusability
of catalyst on the oxidation of benzyl alcohol were investigated
as a model substrate toward the corresponding products. As a
result, 20 mg of Fe2 O3 /SBA-15 were used with H2 O2 in water at
80 ◦ C for 3.5 h in the oxidation of alcohol. Under optimum reaction
conditions, Fe2 O3 /SBA-15 showed highest catalytic activity with
95% conversion of benzyl alcohol to benzaldehyde. Fe2 O3 /SBA-15
exhibited an excellent catalytic performance in the oxidation sul-
fides to sulfoxides without further oxidation to the sulfone under
the same reaction condition.
As alternative supports, two types of aluminosilicates namely
Al-MCM-41 and Al-SBA-15 were used as support to stabilize iron
Fig. 24. Overall schematic reaction for oxidation of alcohols and sulfides by
Fe2 O3 /SBA-15 catalyst [152].
oxide NPs [153]. Characterization of as-prepared nanomaterials
with XRD and other techniques demonstrated presence of the
hematite phase (Fe2 O3 , JCPDS card 39-0664) in the structure of the
catalysts. The activity of these catalysts was also investigated in the
oxidation reaction of alcohols toward the corresponding carbonyl
compounds under inert condition. Experimental results showed
that both catalysts work efficiently in the oxidation of benzylic
alcohols with either electron-donating or electron-withdrawing
substituents as well as in less sterically-favored positions within
the aromatic ring with over 90% efficiency. Unfortunately, conver-
sions were relatively low in the case of linear alcohols which were
attributed to acid-catalyzed intermolecular etherification between
the two linear alcohol molecules which was in direct competition
with the oxidation reaction.
Wang and coworkers prepared Fex O supported on SBA-15 and
used it for oxidation of propylene in the presence of nitrous ox-
ide [154]. They successfully altered the reaction pathway from
production of acrolein to propylene oxide. Conversely, the main
product was acrolein when the oxidation of propylene was carried
out with Fex O/SBA-15. Modification of Fex O/SBA-15 with alkaline
earth metal salts led only to the formation of propylene oxide
(PO) [155], as depicted in the reaction pathway of Fig. 25.
The nature of the alkali metal ion had a direct influence on
PO selectivity, conversion and turnover frequency (TOF). Differ-
ent alkali metal ions were tested for the oxidation of propy-
lene by Fex O/SBA-15 catalyst. It was demonstrated that PO se-
lectivity and yield increased in the following order: KCl > NaCl >
RbCl > CsCl > LiCl. Experimental results showed that the product
selectivity in the oxidation of propylene over KCl–Fex O/SBA-15
was 76, 1.8 and 1.1% toward PO, acrolein and allyl alcohol, respec-
tively. KCl as an efficient modifier played a key role via interaction
with iron species in the oxidation of propylene toward PO. In
other words, this interaction not only decreased the lattice oxygen
associated with iron species, but also eliminated the surface acidity
originated from iron species. Most importantly, KCl altered the
local coordination of iron structure.
 A. Akbari et al. / Nano-Structures & Nano-Objects 14 (2018) 19–48 37

Fig. 25. Reaction pathway for oxidation of propylene by Fex O/SBA-15 with and without modification by KCl [155].

Fig. 26. Schematic illustration of coalescence and interaction of Fe2 O3 with TiO2 nanomaterials [156].

As another interesting support, titanium dioxide (TiO2 ) was
found to be a good candidate because of its high chemical stability,
strong metal–support interaction, and acid–base property [156].
Recently, TiO2 anatase with three different morphologies namely,
nanoparticles (NP), nanofibers (NF) and nanotubes (NT) were pre-
pared and used as supports with Fe2 O3 NPs (1, 3, 5 and 7 mol%
Fe). The catalytic performance of as-prepared iron oxide supported
TiO2 nanomaterials was tested for liquid phase oxidation of ben-
zyl alcohol under a variety of reaction conditions. The optimum
reaction condition was 0.05 g of catalyst in the presence of 60
mmol H2 O2 at 100 ◦ C for 6 h was which resulted in highest conver-
sion and selectivity toward benzaldehyde. All synthesized Fe2 O3 –
TiO2 nanomaterials showed catalytic activity in the oxidation of
benzyl alcohol with different efficiencies. Among them, iron oxide
supported on TiO2 NPs showed the best performance. It is worth
mentioning that the interaction between Fe2 O3 NPs and TiO2 -NPs,
NTs, NFs played a significant role on their application as catalysts,
as depicted in Fig. 26.
As can be seen in Fig. 26, individual Fe2 O3 NPs had maximum
interaction with TiO2 NPs. On the other hand, the volume available
for interaction (confinement effect) between these NPs was higher
than TiO2 -NTs and TiO2 -NFs with Fe2 O3 NPs. Moreover, the TiO2 -
NP support not only increased the specific surface area but also
increased the number of Lewis acid sites.
Soni and coworkers utilized zirconium oxide (ZrO2 ) NPs as a
stable support in the preparation of iron oxide based catalysts
(Fe2 O3 –ZrO2 ) [157]. In the aforementioned study, the modified
sol–gel method with citric acid and the co-precipitation method
were employed in order to synthesize nanostructured Fe2 O3 –
ZrO2 (18 nm) and bulk Fe2 O3 –ZrO2 (120 nm)catalysts, respectively.
The catalytic potential of as-prepared catalysts was investigated
for the oxidation of dimethyl sulfide (DMS) in the presence of
ozone. Citric acid as a chelating agent played a critical role in the
preparation of nanostructured Fe2 O3 –ZrO2 with the size of 18 nm
via the modified sol–gel method. Experimental results revealed
that the rate of DMS adsorption and oxidation over nanostructured
38 A. Akbari et al. / Nano-Structures & Nano-Objects 14 (2018) 19–48
Fig. 27. Aerobic oxidation of benzoin to benzyl over Fe3 O4 MNPs catalyst [160].
Fe2 O3 –ZrO2 was faster than that over the bulk Fe2 O3 –ZrO2 . This
high activity of nanostructured Fe2 O3 –ZrO2 can be related to its
high specific surface area, narrow particle size distribution, and
high concentration of acid sites.
In another report, Huang et al. utilized porous Fe3 O4 NPs for
epoxidation of styrene with TBHP [158]. To synthesize porous mag-
netic Fe3 O4 NPs, FeCl3 ·6H2 O and hydrazine hydrate were mixed in
ethylene glycol (EG) and heated at 200 ◦ C for 10 h. Additionally,
Au NPs were deposited on as-prepared porous Fe3 O4 in the pres-
ence of L-cysteine and used it as an efficient catalyst for selective
epoxidation of styrene in various organic solvents. A reasonable
mechanism has been described for the formation of Fe3 O4 NPs with
a porous structure. In this mechanism, EG and hydrazine hydrate
had a crucial role as solvent and reducing agent, respectively. In
this process, hydrazine hydrate released N2 and NH3 by reducing
Fe3+ into Fe2+ leading to the reaction of NH3 with water and the
production of hydroxyl ions. Further reaction of Fe3+ and Fe2+ with
hydroxyl ions under hydrothermal condition resulted in the forma-
tion of Fe3 O4 particles. The viscosity of EG as well as insolubility
of N2 in EG lead to the formation of gas bubbles which acted as a
template in the formation of porous Fe3 O4 particles. Epoxidation
of styrene toward styrene oxide as a model reaction was carried
out in the presence of porous Fe3 O4 and Au/L–Fe3 O4 . Experimental
results showed 43.1% conversion and 74.1% selectivity to styrene
oxide within 13 h in acetonitrile in the case of porous Fe3 O4 as
catalyst. In contrary, immobilization of Au onto the porous Fe3 O4
particles enhanced catalytic activity of the catalyst by 76.1% and
70.1% for conversion and selectivity, respectively.
In one study, Wang and coworkers compared the catalytic per-
formance of three different iron oxides, i.e. Fe3 O4 , FeO and Fe2 O3 ,
in epoxidation of alkenes [159]. They selected the epoxidation of
styrene as a model reaction in the presence of molecular oxygen
as an oxidant. The preliminary findings showed that Fe3 O4 had
highest efficiency with 38% conversion and 56.5% selectivity. FeO
had lower specific surface area and showed a lower activity. Fe2 O3
had similar specific surface area to Fe3 O4 but it was almost inactive
for the reaction. Existence of Fe2+ in the crystalline structure of
Fe3 O4 was assumed to be the reason for higher activity of Fe3 O4 in
epoxidation of styrene in the presence of O2 .
Ferrous ammonium sulfate (NH4 )2 Fe(SO4 )2 and ferric chloride
(FeCl3 ) were used as starting materials in the preparation of
Fe3 O4 magnetic nanoparticles (MNPs) via simple co-precipitation
method in alkaline medium [160]. The as-synthesized Fe3 O4 MNPs
were utilized as catalyst in the oxidation of benzoin to benzyl (up
to 90%) as a probe reaction in toluene at 80 ◦ C, as shown in Fig. 27.
This optimum reaction condition was achieved after evaluation
of different parameters such as temperature, solvent, oxidant, and
reaction time. It is important to mention that Fe3 O4 MNPs simulta-
neously acted as a heterogeneous catalyst and as an oxidant in the
oxidation of benzoin. The oxidation of other alcoholic substrates
was also tested by Fe3 O4 MNPs. Experimental results demon-
strated that Fe3 O4 MNPs could oxidize efficiently nitro alcohols to
nitro ketones. However, there was no reaction with amino alcohols
in the presence of MNP at 80 ◦ C.
In another report, Sadri and colleagues used the FeCl2 ·4H2 O and
FeCl3 ·6H2 O as precursors for the preparation of Fe3 O4 MNPs using
Fig. 28. Plausible reaction pathway for the formation of MFe2 O4 [163].
simple co-precipitation method in alkaline medium [161]. The as-
prepared Fe3 O4 MNPs were utilized as a magnetically recoverable
catalyst in oxidation of various primary and secondary benzylic
and aliphatic alcohols into their corresponding carbonyl products
in aqueous medium with hydrogen peroxide as an oxidant at
50 ◦ C. Under optimized condition, all reactions afforded the desired
products in good to excellent yields. In addition, the experiments
on reusability of catalysts showed no loss in catalytic activity even
after four runs.
Recently, nanocrystalline spinel ferrites with a composition of
MFe2 O4 (M = Ni and Co) were synthesized by Paul and cowork-
ers. A simple and versatile hydrothermal method was utilized to
synthesize MFe2 O4 by heating the mixed hydroxide (M(OH)2 +
Fe(OH)3 ) precursor obtained by a co-precipitation method
[162,163]. In order to produce small NPs with narrow size dis-
tributions, the investigators used PEG 4000 and tributylamine as
surfactant and hydroxylating agent, respectively. Employing this
strategy led to the synthesis of NiFe2 O4 with size of 2–10 nm and
CoFe2 O4 with size of 2–30 nm. A plausible reaction pathway for the
formation of MFe2 O4 (M = Ni and Co) is illustrated in Fig. 28.
The catalytic potential of as-synthesized nanomaterials was
evaluated in the oxidation of various alcohols to aldehydes by
periodic acid.
2.6. Group 9 elements (Co, Rh and Ir)
2.6.1. Cobalt oxide nanoparticles
Cobalt oxide NPs have received significant attention due to their
applications in many different fields such as electrochemical, gas
sensing and catalysis [164–168]. The size and morphology of metal
oxide NPs are important to their catalytic activity in oxidation re-
actions. There is a strong correlation between the aforementioned
factors and activity as well as selectivity of these catalysts.
In this regard, three different cobalt oxide nano-catalysts were
synthesized using a simple hydrothermal process [169]. Polyhe-
dral oligomeric silsesquioxane (POSS) bearing 16 carboxylic acid
groups which can easily couple to the metal carbonyl groups, was
used as a silica support for cobalt oxide catalyst. Compared to
other silica supports, advantages of POSS NPs [170] include well-
dispersion of cobalt oxide NPs in the structure of POSS based
support which increased catalytic activity of cobalt oxide during
the hydrothermal process and protection of cobalt oxide from
sintering by POSS. Moreover, POSS supported cobalt oxide cata-
lysts have a uniform morphology with a narrow size distribution
 A. Akbari et al. / Nano-Structures & Nano-Objects 14 (2018) 19–48
after calcination. The calcination was carried out in three different
temperatures of 150, 550 and 650 ◦ C which led to labeling the
catalyst as Co3 O4 -150, Co3 O4 -550 and Co3 O4 -650, respectively. The
catalytic performance of these catalysts with different nanocrys-
talline structures was tested in the oxidation reaction of styrene
in the presence of H2 O2 as a green oxidant. Experimental results
demonstrated that morphology and size of cobalt oxide NPs can
be controlled by tuning the synthetic parameters which resulted
in Co3 O4 -550 having extraordinary activity and high selectivity
toward styrene oxide.
In 2014, Beller and coworkers developed a novel cobalt oxide
based heterogeneous catalyst [171]. Wet impregnation method
was used in the presence of cobalt (II) acetate and different types
of ligands bearing nitrogen atoms on Vulcan XC72R followed by
pyrolysis at 800 ◦ C. This system showed excellent oxidation per-
formance in epoxidation of many different types of olefins such as
renewable olefins as well as cholesterol and vitamin derivatives
with excellent chemoselectivity for the respective epoxides.
Synthesis of Co3 O4 nanocrystals with narrow size distribution is
a challenging issue due to their fast precipitation and the formation
of particle agglomerates with unusual shape in synthetic process.
In this regard, a new efficient precipitation method was developed
for preparing cobalt oxide nanocrystals using cobalt nitrate as the
precursor in the presence of N-Cetyl-N,N,N-trimethyl ammonium
bromide (CTAB) and in-situ generated triethylamine salt [172].
Inorganic–organic layered particle model was used for the inter-
pretation of nanocrystal formation. According to this model, the
organic cations which originated from CTAB and in-situ generated
triethylamine salt were adsorbed on the polar surface of metal
oxide particles which separated the NPs from each other by de-
creasing van der Waals interactions between the nanoparticles.
The catalytic activity of these cobalt oxide NPs was compared
with the bulk cobalt catalyst for oxidation of cyclohexane in the
presence of molecular oxygen as an oxidant. In addition, various
parameters such as catalyst amount, different catalyst types, re-
action temperature, reaction time, reusability and stability of the
catalyst were investigated. High conversion and selectivity were
obtained at 393 K at reaction time of 6 h.
Nanostructured cobalt oxide can be inserted in the pores of
mesoporous silica (MCM-41) via ultrasound radiation method. In
one special research, CoO–MCM-41 nano-catalyst was prepared
ultrasonically from cobalt carbonyl, [Co(CO)3 NO], as the precur-
sor [173]. This catalyst was utilized in epoxidation of olefins ac-
cording to Mukaiyama’s method [174] in the presence of isobu-
tyraldehyde as the reductant.
2.7. Group 11 elements (Cu, Ag and Au)
2.7.1. Copper oxide nanoparticles
CuO can be recognized as one of the most important transition
metal oxides in a broad range of material science [175]. Different
synthetic methods lead to the formation of CuO NPs with various
shapes and morphologies such as nanotubes [176], nanorods [177],
hollow microspheres [178], nanospheres [179], aligned nanowires
[180], nanocages [181], microflowers [182] and dandelions [183].
In one report [184], urchin-like CuO NPs with self-assembled
nanostrips were synthesized using a facile reflux method. In this
method, Cu(NO3 )2 ·3H2 O and urea as starting materials were dis-
solved in the mixture of distilled water and ethylene glycol mono-
methyl ether followed by heating the mixture at 100 ◦ C for 6
h. Different copper salt sources and the preparation method af-
fected shape and morphology of the synthesized CuO particles.
On the other hand, unlike copper nitrate, the use copper sulfate
and copper chloride as precursors led to CuO NPs with rod-like
and octahedral shapes, respectively. In the case of preparation
method, it must be mentioned that conventional methods lead to
39
the formation of CuO particles with a cluster shape. In contrary,
commercial CuO is a bulk material and has no specific morphol-
ogy. Moreover, the above research tested the catalytic activity of
these CuO particles with different morphologies in epoxidation of
norbornene in the presence of t-butyl hydroperoxide as an oxidant.
Because of their uniform and organized shapes, the urchin-like CuO
NPs showed excellent catalytic performance with 89.5% conversion
and 100% selectivity compared with other CuO particles. Trans-
stilbene and cis-cyclooctene were also successfully converted to
the corresponding epoxide products with moderate conversion
and high selectivity in the presence of urchin-like CuO NPs as an
efficient catalyst.
As mentioned above, the preparation method and type of cop-
per precursor are two important factors which influence the cop-
per oxides microstructure as well as their catalytic activity. In
this regard, microwave-assisted hydrothermal method was em-
ployed in order to synthesize CuO NPs with different shapes [185].
In this study, urchin-like CuO NPs (CuO-1) were formed under
microwave radiation for 30 min when Cu(OAc)2 /urea was used
as starting material. Interestingly, rod-like nanoparticles (CuO-2)
which self-assembled into flower-like structures were formed by
using Cu(NO3 )2 /urea as the precursor. The mechanism of formation
of these copper oxides was studied by XRD and SEM techniques
and catalytic activity of these two copper oxides were investigated
in epoxidation of olefins in the presence of TBHP. Styrene was
selected as the model reaction and its epoxidation was studied
in detail during 24 h by CuO-1 and CuO-2. Experimental results
showed that 28% selectivity was obtained toward styrene oxide
after 1 h in the case of CuO-1. In contrast, selectivity was almost
zero as CuO-2 was used as the catalyst for 1 h indicating that CuO-
1 with its larger surface area had higher catalytic activity in the
initial stage of the reaction. After 24 h of reaction, styrene was
completely oxidized using both CuO-1 and CuO-2 catalysts. After
8 h of reaction, the conversions of trans-β -methylstyrene reached
97% with selectivity of 100%.
Instability and coagulation of unsupported CuO NPs are impor-
tant issues that limit their catalytic application in oxidation reac-
tions. Consequently, much attention has been focused on the syn-
thesis of supported CuONPs. For example, synthetic Ag nanowires
were used as a support in order to carry CuO NPs [186]. CuO@Ag
nanowires exhibited excellent catalytic performance when used as
a catalyst in both epoxidation of trans-stilbene and oxidation of
various alcohols in the presence of air and tert-butyl hydroper-
oxide (TBHP) as the oxidant, respectively. The effectiveness of
CuO@Ag nanowires as a catalyst in epoxidation of trans-stilbene
was tested in different organic solvents such as DMF, Dioxane,
O-Xylene, toluene and isopropylbenzene. O-Xylene was chosen
as the best solvent with 99% conversion and good selectivity in
this reaction. When O-Xylene was utilized as the solvent, GC–MS
analysis showed 2-methylbenzaldehyde, o-tolylmethanol, and 2-
methylbenzoic acid as byproducts which enabled Cao and cowork-
ers to propose a logical reaction mechanism. The reaction mecha-
nism is depicted in Fig. 29. As seen in Fig. 29, O-Xylene has a crucial
role in the formation of unstable free radical intermediates with
active oxygen on the surface of CuO@Ag nanowires. Subsequently,
peroxide is formed and used as an oxidant in the epoxidation of
trans-stilbene.
In addition, the versatility of CuO@Ag nanowires as the catalyst
was investigated in the oxidation of alcohols to the corresponding
aldehydes, carboxylic acids or ketones in the presence of TBHP and
acetonitrile as oxidant and solvent, respectively.
Sumitomo process [187] has been known as practical method
for the preparation of propylene oxide from propene. In this
method, cumene (CUM) is used to produce cumyl hydroper-
oxide (CHP) to promote the epoxidation reaction. Ravasio and
coworkers utilized this method in the presence of CuO/Al2 O3 bi-
functional nanomaterials as the catalyst [188]. Highly dispersed
40 A. Akbari et al. / Nano-Structures & Nano-Objects 14 (2018) 19–48
Fig. 29. The role of O-Xylene in epoxidation of trans-stilbene over CuO@Ag nanowires [186].
CuO/Al2 O3 NPs were synthesized with a very small crystallites size
by chemisorption–hydrolysis method. Then the catalytic activity
of these NPs was studied in one-pot epoxidation of some olefins.
Reaction scheme for epoxidation of trans-stilbene is shown in
Fig. 30.
For comparison, bare Al2 O3 and CuO/SiO2 were also used as
catalysts in the epoxidation reactions. Results showed that these
materials are poorly active or fully inactive, suggesting that Al2 O3
and CuO have a synergistic effect in the oxidation reaction. Ad-
ditionally, the stability and reusability experiments showed that
the CuO/Al2 O3 catalyst can be used for more than 3 times in the
conversion of stilbene to the corresponding epoxide with only a
slight loss of catalytic activity.
Epoxidation of styrene to styrene oxide was also studied by
supported copper oxide in the presence of TBHP. In one report, the
catalytic effect of different CuO supports such as CuO/Si-MCM-41,
CuO/Al2 O3 , CuO/Ga2 O3 and CuO/In2 O3 was investigated [189]. Fur-
ther, anhydrous or aqueous TBHP significantly affected selectivity
and yield of the products. Other studies showed that the CuO/In2 O3
catalyst had better performance in epoxidation by anhydrous TBHP
but the catalytic activity of CuO/Ga2 O3 was better in epoxidation
by aqueous TBHP. Otherwise, CuO/SiO2 had better performance in
epoxidation by both anhydrous and aqueous TBHP.
The low catalytic activity of SiO2 supported copper oxide,
CuO/SiO2 , was reported in the epoxidation reaction [188]. Using
alkali metal ions as a promoter can be considered a novel strat-
egy to improve the catalytic activity of CuOx /SiO2 . For instance,
Wang and colleagues utilized Cs+ as the most efficient promoter
of CuOx /SiO2 for epoxidation of propylene to propylene oxide by
O2 [190]. The sol–gel method was used for preparation of Cs+ -
modified CuOx /SiO2 catalyst. In this process, an aqueous solution
of Cs+ ion was mixed with the aqueous solution of Cu(NO3 )2 in
the presence of ethylene glycol followed by dropwise addition of
tetraethyl orthosilicate. The final product as catalyst was obtained
after calcination for 6 h at 823 K. For comparison, the catalytic
performance of different alkali-metal-ion-modified CuOx /SiO2 was
also investigated. Results demonstrated that only the selectivity to
PO increased by changing the alkali ion from Li+ to Cs+ and there
was no obvious trend in the change of propylene conversion. In the
aforementioned study, the Cs/Cu molar ratio and reaction temper-
ature were also studied in detail to optimize reaction conditions.
The highest PO yield was obtained with a Cs/Cu ratio of 0.4. Based
on kinetic studies, the reaction pathways shown in Fig. 31A and
31B are proposed for the oxidation of propylene by CuOx /SiO2 and
Cs+ -modified CuOx /SiO2 , respectively. The oxidation of propylene,
as a substrate occurred in both vinyl and allyl positions to give
PO and acrolein as the primary products. Based on Fig. 29A, these
primary products were obtained with CuOx /SiO2 as the catalyst in
the presence of O2 . The isomerization of PO to allyl alcohol followed
by oxidation to acrolein is recognized as the drawbacks of working
with CuOx /SiO2 as the catalyst which significantly decreased the
PO yield. In the case of Cs+ -modified CuOx /SiO2 , the existence of
Cs+ not only prevented the consecutive conversion of PO but also
increased the selectivity to PO and yield of acrolein, as depicted in
Fig. 31.
The same authors reported other copper oxide based catalytic
systems such as CuOx /SBA15 and CuOx -SiO2 modified by K+ which
were used in the oxidation of propylene to propylene oxide
[191–193].
 A. Akbari et al. / Nano-Structures & Nano-Objects 14 (2018) 19–48 41

Fig. 30. trans-stilbene epoxidation by CuO/Al2 O3 catalyst [188].

Fig. 31. Reaction pathways for oxidation of propylene by O2 : (A) in the presence of CuOx /SiO2 and (B) in the presence of Cs+ -modified CuOx /SiO2 [190].
42 A. Akbari et al. / Nano-Structures & Nano-Objects 14 (2018) 19–48
Fig. 32. Reaction pathways for preparation of copper complexes anchored onto SBA-15 and copper oxide nanoparticles immobilized onto SBA-15 [194].
As exhibited in Fig. 32, two new SBA-15-supported copper
oxides were synthesized and utilized for the oxidation of benzyl
alcohol in the presence of H2 O2 as an oxidant [194].
As seen from Fig. 32, CuO/SBA-15-C1 was prepared directly by
the reaction of Cu (II) ions with surface silanol groups onto silica
followed by calcination at 500 ◦ C. But in the case of CuO/SBA-15-C2
SBA-15 was treated first by 3-[bis[(2-hydroxyethyl)amino] propyl-
triethoxysilane] (PADOH) and Hexamethyldisilazane (HMDS) to
produce Cu(II)-PADO-HMDS-SBA-15. Then, the as-prepared mate-
rial was calcined at 500 ◦ C. It must be highlighted that the forma-
tion of oligomeric copper spices which produce metallic aggregates
did not occur when the surface of SBA-15 was modified with
PADOH and HMDS. The catalytic performance of these materials
for the title reaction showed 83% and 82% selectivity toward ben-
zaldehyde over CuO/SBA-15-C1 and CuO/SBA-15-C2, respectively.
Recently, new bimetallic oxide systems based on copper oxide
are the subject of ongoing research. In one report, an efficient NiO
promoted CuO–NiO/SBA-15 catalytic system was developed using
the ultrasonic post-grafting method [195]. SBA-15, with amine
groups on its internal surfaces, can absorb the starting materials
into its mesoporous channels under ultrasonic conditions. In this
system, NiO not only improved the distribution of CuO–NiO in the
mesoporous channels of SBA-15, but also increased the catalytic
activity of copper oxide. The catalytic activity of CuO–NiO/SBA-15
was compared with other catalysts such as CuO/SBA-15, NiO/SBA-
15 and SBA-15 in the epoxidation of styrene as a model reaction
in the presence of TBHP. In the case of monometallic species like
CuO/SBA-15 and NiO/SBA-15, the conversion, selectivity and the
yield of this reaction was low. Interestingly, the conversion and
selectivity of styrene to styrene oxide improved to 73.6% and 83.2%,
respectively, with the incorporation of NiO. These preliminary
results demonstrated an obvious synergistic effect in NiO–CuO
system. Moreover, the molar ratio of Ni/Cu affected the conversion,
selectivity and yield of this reaction. CuO–NiO/SBA-15 with 0.34
molar ratio of Ni/Cu had the best catalytic performance with 100%
conversion and 92.3% selectivity. Other olefins such as norbornene,
trans-β -methylstyrene, trans-stilbene and cis-cyclooctene were
also oxidized in the presence of CuO–NiO/SBA-15 catalyst. Olefins
bearing electron-donating substitutes can absorb onto the vacant
coordination sites of metal oxides and increase the activity of
the double bonds of the olefins [196]. The order of reactivity
was trans-stilbene > trans-β -methylstyrene > norbornene > cis-
cyclooctene. In the proposed mechanism, the olefin substrate and
TBHP were absorbed into the channels and on the metal oxide
surface, respectively. Next as shown in Fig. 33, oxametallacycle
was formed via insertion of peroxidic groups between secondary
carbons of the neighboring adsorbed styrene molecules. Oxamet-
allacycle underwent two different pathways simultaneously. One
pathway was the rearrangement to form styrene oxide and the sec-
ond pathway was the reaction with radicals to get benzaldehyde.
The second pathway can be eliminated by the addition of Na2 CO3
as a hydroxyl radical scavenger which increased the conversion of
styrene and selectivity for styrene oxide.
For the first time, Pande and coworkers developed a new
method to synthesize nanocomposites of CuO and Cu(0) supported
on cation exchange resin-bound NPs [197]. In this approach, CuSO4
aqueous solution was employed as the Cu2+ ions precursor which
exchanged H+ with the cationic resin. Depending on the type of re-
ducing agent, Cu(0) or CuO could be produced on the resin matrix.
Conversely, Cu(0) was produced by using aqueous borohydride or
hydrazine and surprisingly CuO was obtained with an alkaline so-
lution of cyclodextrin (CD). In this case, CD not only facilitated the
formation of CuO by decreasing the activation energy, but also con-
trolled the growth of CuO NPs with its capping property [198]. The
catalytic activity of as-prepared catalysts was investigated for the
oxidation of various alcohols in air. Experimental results demon-
strated that the CuO nanocomposite has a remarkable efficiency
compared to the corresponding Cu(0) and commercial CuO. The
aggregation tendency of nanoparticle catalysts is a major obstacle
for their practical use under catalytic reactions. In one report, well-
dispersed CuO colloidal nanocrystal clusters (CNCs) were prepared
by a simple one-pot solvothermal method and used for olefin
epoxidation in the presence of TBHP as an oxidant [199]. In order
to prevent the aggregation of CuO CNCs as well as to improve their
stability, mesoporous SiO2 was utilized as a protective coating shell
to form CuO CNCs@meso-SiO2 nanocomposites. Fig. 34 depicts the
synthetic scheme of CuO CNCs@meso-SiO2 nanocomposites.
The catalytic performance of CuO CNCs@meso-SiO2 nanocom-
posites were compared with CuO CNCs and Cu2 O hollow
nanospheres for norbornene epoxidation using TBHP and ace-
tonitrile as the oxidant and solvent, respectively. All catalysts
had 100% selectivity for norbornene epoxidation to the corre-
sponding product. But the conversion was 90, 86 and 82.3% using
CuO CNCs@meso-SiO2 nanocomposites, CuO CNCs and Cu2 O hol-
low nanospheres, respectively. Additionally, epoxidation of other
olefins were also tested in the presence of these catalysts. The
CuO CNCs@meso-SiO2 nanocomposites showed excellent catalytic
performance even after eight runs.
Recently, Wang and colleagues developed a new copper oxide
based hybrid nano-catalyst which consisted of iron oxide mag-
netic NPs (Fe3 O4 ) and mesoporous silica (meso-SiO2 ) as the core
and protective shell, respectively [200]. The synthetic process for
Fe3 O4 –CuO@meso-SiO2 microspheres is illustrated in Fig. 35.
 A. Akbari et al. / Nano-Structures & Nano-Objects 14 (2018) 19–48 43

Fig. 33. Oxidation mechanism of styrene to benzaldehyde over CuO–NiO/SBA-15 [196].

Fig. 34. Schematic illustration of the synthetic pathway of CuO CNCs and CuO CNCs@meso-SiO2 nanocomposites [199].

Fig. 35. Synthetic process of the Fe3 O4 –CuO@meso-SiO2 microspheres [200].

Briefly, a one-step solvothermal method was utilized to modify
Fe3 O4 NPs with polyacrylic acid (PAA). The existence of carboxylic
acid groups on the surface of Fe3 O4 facilitated the deposition of
copper ions in the presence of PVP and urea. Finally, a template-
assisted sol–gel technique was used to deposit a silica protective
shell. Fe3 O4 –CuO@meso-SiO2 microspheres showed excellent per-
formance in the epoxidation of olefins in the presence of TBHP as
a green oxidant in acetonitrile. Fe3 O4 and SiO2 played critical roles
in catalytic activity of Fe3 O4 –CuO@meso-SiO2 . On the other hand,
Fe3 O4 not only facilitated separation of catalyst from the reaction
mixture by an external magnet but also promoted catalytic activity
of the catalyst with its electron-donating properties [201]. The
SiO2 layer with its mesoporous structure inhibited aggregation
of NPs via a physical protective shell. Moreover, the small size
of the pores of the silica shell compared with CuO and Fe3 O4
prevented CuO and Fe3 O4 from leaching. It is worth highlighting
that mesoporous SiO2 with ordered channels acts as nano-reactors
by adsorbing reagents and accelerating the mass transfer. To inves-
tigate the general applicability of the Fe3 O4 –CuO@meso-SiO2 cata-
lyst, some other olefin derivatives were also studied. Experimental
44 A. Akbari et al. / Nano-Structures & Nano-Objects 14 (2018) 19–48

Table 1
Summary of results for transition metal oxide based catalysts in oxidation reactions.
Transition metal oxide based catalysts Starting materials Oxidation conditions Products Refs
TiO2 Secondary alcohols Solvent: PEG400 Ketones [46]
Oxidant: H2 O2
Rutile TiO2 nanorods Benzyl alcohol Solvent: Acetonitrile Benzaldehayde [48]
Irradiation of Xenon Lamp
RuO2 /TiO2 nanobelt Benzyl alcohol UV and visible light irradiation Benzaldehayde [55]
TiO2 /Graphene Benzyl alcohol Visible light irradiation Benzaldehayde [60]
TiO2 /carbon nanotubes
TiO2 /fullerene
AgBr@TiO2 /GO Benzyl alcohol Visible light irradiation Benzaldehayde [62]
TiO2 with 2D, 3D ordered mesoporous Various alcohols UV-irradiation Various ketones [63]
SiO2 /TiO2 Benzyl alcohol Various bronsted acid Benzaldehayde [64]
UV-irradiation
WO3 /TiO2 Benzyl alcohol 450 W high-pressure mercury Benzaldehayde [66]
lamp
M–TiO2 , M=Cr3+ , Mn2+ , Fe3+ , V5+ ,Zn2+ , Benzyl alcohol Oxidant:tert-butyl Benzaldehayde [67]
Ni2+ , Ag+ , Cu2+ and Co2+ hydroperoxide (TBHP)
Vanadium doped TiO2 Benzyl alcohol Solvent: methanol Benzaldehayde [68]
Oxidant: H2 O2
TiO2 nanotubes Hydrocarbons Solvent-free Various products [70]
TiO2 nanofibers
Anatase, Rutile, and Brookite TiO2 5-(Hydroxymethyl)- Water 2,5-furandicarbaldehyde [71]
2-furaldehyde
V2 O5 /SiO2 Propene UV-irradiation Propene oxide [72]
V2 O5 /Al2 O3 Methanol – Formaldehyde [73]
V2 O5 /Al2 O3 Formaldehyde Air Formic Acid [77]
100 ◦ C
V2 O5 /Al2 O3 Cyclohexane Co-catalyst : Pyrazine Cyclohexanone [80]
V2 O5 /SiO2 2-carboxylic acid
V2 O5 /TiO2
V2 O5 @TiO2 Cyclohexane Solar light irradiation Cyclohexanone [83]
V2 O5 /WO3 Cyclohexane Oxidant: H2 O2 Cyclohexanone [84]
Room Temperature
MoO2 Olefins Oxygen donors: tert-butyl Epoxides [91]
hydroperoxide (TBHP)
Fe-doped MoO2 Olefins Various Solvents and Oxidants Epoxides [92]
α-Fe2 O3 /MoO2 Olefins Carbon tetrachloride (CCl4 ) Epoxides [93]
Oxidant:tert-butyl peroxide
(tBuOOH)
MoO2 Liquid hydrocarbons 850 ◦ C and 1 atm Corresponding product [100]
MoO3 /ZrO2 Cyclooctene TBHP as an oxidant Epoxide product [103]
MoO3 /TiO2
MoO3 /SiO2
MoO3 /TiO2 Allyl acetate TBHP as an oxidant Epoxide product [105]
MoO3 /SiO2
Fe–MoOx/PANI nanorods Cyclooctene TBHP as an oxidant Epoxide product [108]
γ-Fe2 O3 @C@MoO3 Cyclooctene Oxidant:tert-butyl peroxide Epoxide product [110]
(tBuOOH)
WO3 -MCM-48 Sulfides Oxidant: H2 O2 Sulfoxides [111]
WO3 /SBA-15(OA) Cyclopentene Oxidant: H2 O2 Glutaraldehyde [113]
WO3 /SBA-15(HP)
WO3 /SBA-15(AM)
WO3 -MCF Cycloocta-1,5-diene Oxidant: H2 O2 Epoxide product [116]
W–X/SnO2 , X=Li, Na, K, Rb, Cs, Mg, Ca, Sr, 1-hexene Oxidant: H2 O2 Epoxide product [117]
Ba, Y, La, Ce, Pr, Sm, Eu, Dy, Yb, Ni, Cu, Ag,
Zn, Cd, Ga, and In
MnO2 /GO Benzyl alcohol Oxidant: Air Benzaldehyde [120]
MnO2 Benzylic alcohols Solvent: Acetonitrile Corresponding aldehydes [121]
Oxidant: H2 O2
Ca0.16 MnO2 ·2H2 O Benzyl alcohol Solvent: Acetonitrile Benzaldehayde [122]
Oxidant: O2

(continued on next page)

 A. Akbari et al. / Nano-Structures & Nano-Objects 14 (2018) 19–48 45

Table 1 (continued)
Transition metal oxide based catalysts Starting materials Oxidation conditions Products Refs
MnO2 /OMS-2 5-hydroxymethylfurfural 0.5 MPa O2 2,5-diformylfuran [124]
Mn2 O3 Alcohols PhI(OAc)2 Aldehydes [126]
MnO Styrene Oxidant: H2 O2 Epoxide product [131]
Mn2 O3 Cyclohexene or styrene Solvent: Acetonitrile Epoxide product [132]
Oxidant: tert-butyl
hydroperoxide (TBHP)
Au/Ag/MnOx Olefins Oxidant: H2 O2 Epoxides [138]
γ-MnO2 octahedral molecular sieves Toluene Atmospheric reflux Benzoic acid [142]
Oxidant:molecular oxygen
δ-MnO2 Formaldehyde – CO2 [146]
nano-γ-F2 O3 Benzyl alcohol Oxidant: H2 O2 Benzaldehyde [148]
α-Fe2 O3 Methyl phenyl sulfide ultrahigh-pressure (UHP) Sulfoxide product [149]
α-F2 O3 Styrene Oxidant: tert-butyl Epoxides [151]
hydroperoxide (TBHP)
Fe2 O3 /SBA-15 Alcohols and sulfides Oxidant: H2 O2 Corresponding [152]
products
KCl–Fex O/SBA-15 Propylene Nitrous oxide Acrolein [155]
Fe2 O3 –TiO2 Benzyl alcohol Oxidant: H2 O2 Benzaldehyde [156]
Fe2 O3 –ZrO2 Dimethyl sulfide (DMS) Ozone Atmosphere Sulfoxide product [157]
porous Fe3 O4 Styrene Oxidant: tert-butyl Epoxides [158]
hydroperoxide (TBHP)
Fe3 O4 Primary and secondary Oxidant: H2 O2 Corresponding [161]
benzylic and aliphatic alcohols carbonyl products
Co3 O4 -150, Co3 O4 -550 and Co3 O4 -650 Styrene Oxidant: H2 O2 Epoxides [170]
Co3 O4 nanocrystals Cyclohexane Oxidant: molecular oxygen Corresponding [171]
products
CoO-MCM-41 Oefins – Epoxides [173]
urchin-like CuO Norbornene Oxidant: tert-butyl Epoxides [184]
hydroperoxide (TBHP)
CuO@Ag nanowires trans-stilbene Oxidant: air Epoxides [186]
CuO/Al2 O3 trans-stilbene cumylhydroperoxide (CHP) Epoxides [188]
CuO/Si-MCM-41, CuO/Al2 O3 , CuO/Ga2 O3 Styrene Oxidant: tert-butyl Epoxides [189]
and CuO/In2 O3 hydroperoxide (TBHP)
CuOx /SiO2 Propylene Oxidant: air Propylene oxide [190]
CuOx /SBA15 Benzyl alcohol Oxidant: H2 O2 Benzaldehyde [194]
CuO–NiO/SBA-15 Styrene Oxidant: tert-butyl Epoxides [195]
hydroperoxide (TBHP)
CuO–NiO/SBA-15 Olefins Oxidant: tert-butyl Epoxides [196]
hydroperoxide (TBHP)
CuO CNCs@meso-SiO2 nanocomposites Olefins Oxidant: tert-butyl Epoxides [199]
hydroperoxide (TBHP)
Fe3 O4 –CuO@meso-SiO2 microspheres Olefins Oxidant: tert-butyl Epoxides [200]
hydroperoxide (TBHP)
CuO nanorods Olefins Oxidant: tert-butyl Epoxides [202]
hydroperoxide (TBHP)
CeO2 para-xylene Oxidant: air Terephthalic acid [203]
CeO2 nanocubes para-xylene Oxidant: air Terephthalic acid [204]

results showed high conversion and excellent selectivity for epox-
ide products. These unique properties of Fe3 O4 –CuO@meso-SiO2
catalyst originates from synergistic effects of Fe3 O4 , CuO and
SiO2 .
As mentioned previously, the morphology and shape of NPs
as a catalyst play a crucial role in their catalytic activity. For ex-
ample, CuO nanorods were obtained using a simple hydrothermal
protocol [202] and the as-prepared CuO nanorods were used as a
catalyst in the oxidation of cyclohexene in the presence of TBHP
in acetonitrile. Surprisingly, as shown in Fig. 36, a nearly 100%
cyclohexene conversion with 95% selectivity of 2-cyclohexene-1-
one was achieved. Conversely, less than 5% selectivity of the epoxy
product was achieved.
2.8. Other metal oxides
2.8.1. Cerium oxide nanoparticles
Cerium dioxide NPs (CeO2 NPs) with an average size of 15 nm
was synthesized and employed as an environmentally friendly
heterogeneous catalyst for the aerobic oxidation of para-xylene
to terephthalic acid in water by Deori and coworkers [203]. The
catalytic activity of as-prepared CeO2 NPs was compared with the
commercially available bulk CeO2 materials. The highest activity
of CeO2 NPs could be related to their small crystallite size (15 nm)
which provided a very high surface area as well as a large number
of pores. Additionally, Cetyl tri-methyl ammonium bromide (CTAB,
99%) was used as an ionic surfactant in the preparation of CeO2 NPs
46 A. Akbari et al. / Nano-Structures & Nano-Objects 14 (2018) 19–48
References
Fig. 36. Cyclohexene oxidation over CuO nanorods in the presence of TBHP [202].
which not only could bind to CeO2 NPs surface via its ionic chain-
end but also facilitated the interaction of para-xylene with catalyst
via its hydrophobic tail.
The method of nanoparticle synthesis plays a critical role on
size and surface morphology. For instance, the same authors syn-
thesized three-dimensional self-assembled CeO2 nanocubes and
utilized them as an efficient catalyst in the oxidation of para-
xylene to terephthalic acid [204]. Various reaction parameters such
as the types of surfactant and solvent, reaction temperature and
time affected the self-aggregation of small nanocrystallites for the
formation of CeO2 nanocubes. CeO2 nanocubes formed using oleic
acid as the surfactant and octadecene. The shape and size of CeO2
nanocrystals depended on the reaction time and temperature. On
the other hand, upon increasing the reaction time from 15 to 60
min, the average size of the nanocube increased from 15 to 45
nm at 300 ◦ C. The experimental results demonstrated that the
as-prepared catalyst quantitatively converted the para-xylene to
terephthalic acid with absolute selectivity within 20 h at 70 ◦ C or
within 18 h at 85 ◦ C.
It is worth mentioning that the effects of crystal shape and
surface property of two types of CeO2 NPs (Oleic acid-coated CeO2
nanocubes and irregular CeO2 NPs) on their catalytic activity for
selective oxidation of toluene to benzaldehyde were investigated
previously [205]. Oleic acid not only acted as a surfactant in the
synthesis of CeO2 nanocubes but also increased the conversion
of toluene to benzaldehyde in water using its hydrophobic tail
which facilitated the contact of toluene with the surface of CeO2
nanocubes.
Table 1 summarizes some of the catalytic properties of tran-
sition metal oxide based catalysts in oxidation reactions. More
details on the reaction conditions can be found in the relevant
references.
3. Conclusion and outlook
In this review, we have shown how transition metal oxide NPs
can be used as advanced catalysts for a wide variety of oxidation
reactions such as epoxidation and oxidation of sulfides, alcohols
and alkanes. Increasing concerns about environmentally friendly
and sustainable processes have driven catalytic research with
transition metal oxide nanoparticles toward oxidation reactions
in recent years. Therefore, this review can provide information
to chemists related to (a) different synthetic pathways for the
production of similar crystalline phases with different surface area,
pore volume, pore diameter, surface defect, porosity, particle size,
and catalytic activities and (b) the performance of transition metal
oxide NPs for oxidation reactions without using a ligand or other
reagents.
Acknowledgments
Authors thank the Research Council of the University of
Maragheh (M. A), the University of Bonab (A. A), and the Iran
Science Elites Federation (ISEF) for financial support of this work.
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