Transition Metal Oxide Nanoparticles As Efficient Catalysts in Oxidation

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: [email protected] (A. Akbari), [email protected] (M. Amini), [email protected] (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

currently use Microsystems. Toward this end, an updated com-
Nowadays, oxidation reactions play a substantial role in mod- prehensive review on transition metal oxide NPs for catalysis of
ern chemistry as well as chemical industry. Around 30% of total oxidation reactions has not been published until now. The focus
production in the chemical industry is carried out by the oxida- of this review is to discuss the scope and limitations of transition
tion process. It means that after polymerization, oxidation is the metal oxide NPs as an efficient catalyst for the oxidation of various
largest process in the production of chemicals [1–12]. On the other organic substrates, such as olefins, alcohols, alkanes and sulfides.
hand, many intermediates such as alcohols, epoxides, aldehydes, However the application of transition metal oxides as a support
ketones and organic acids are obtained via oxidation catalysis [2– is not covered here. Consequently, this review mainly covers the
10,13–23]. From point of view of green and sustainable chemical literature published during the past 20 years and is divided into
processing, oxidation reaction has been known as an important eight main sections based on the transition metal group number.
reaction for enhancing the formation of selective products in com- In each section, the articles are chronologically ordered according
parison with non-selective reactions. On the other hand, in order to metal type.
to increase the selectivity, optimization of the catalyst process
conditions are needed which satisfy the principles of green chem- 2. Transition metal oxide nanoparticles
istry [24–27]. As a result, design and development of new catalytic
oxidation processes is essential for laboratories and industries. 2.1. Group 4 elements (Ti, Zr and Hf)
As an example of green oxidation, the catalytic oxidation of
organic substrates to selective products has been known as one of 2.1.1. Titanium oxide nanoparticles
the most important chemical transformations in organic synthesis. TiO2 NPs are well known as a photocatalyst and have been
In this reaction, permanganate and dichromate were utilized as widely utilized for photochemical applications such as, degrada-
traditionally oxidizing reagents but they are expensive, toxic and tion of organic and inorganic pollutants [41,42], solar cells [43,44],
generate to a large quantity of heavy-metal waste. Heterogeneous organic transformations and hydrogen production by water split-
catalytic systems use O2 or air as a simple and safe oxidant and ting [45]. Oxidation reactions as an important organic transforma-
produce water as the sole by-product which not only solve the tion using TiO2 NPs have attracted much attention. In most cases,
above aforementioned problems but also follow the principles of TiO2 NPs were used as photo-degradation materials.
green and sustainable chemical processes [28–30]. Over the last
few years, considerable efforts have been devoted to the field of 2.1.1.1. Alcohols oxidation. Although TiO2 NPs have photo-degra-
nanotechnology [31–36] and nano-science especially at the inter- dation capacity, a significant volume of research has been recently
face of metal and metal oxide nanoparticles (NPs) due to their carried out in selective oxidation of organic substrates such as
relatively high chemical activity as well as specificity of interaction. alcohols, amines, aromatic alkanes and cyclohexanes by TiO2 in
These nano-sized materials in comparison to their bulk equivalents the presence of O2 under UV–Vis irradiation. For instance, a green
have many different properties such as a large surface-to-volume oxidation method was developed for the oxidation of secondary
ratio [37]. Among all the materials to be prepared on the nanoscale, alcohols to corresponding ketones by Kidwai and coworkers [46].
transition metal oxides are noteworthy candidates from a scientific In this protocol, TiO2 NPs were used as a heterogeneous catalyst in
as well as a technological point of view [38,39]. Transition metal the presence of polyethylene glycol (PEG 400) as a green solvent
oxides can exhibit unique characteristics which make them the and H2 O2 as an oxidative regent. For the possible reaction mecha-
most versatile class of materials with properties covering all as- nism, they proposed the production of superoxide species O−2 over
pects of solid state and materials science [40]. Oxidation reactions TiO2 NPs. As it can be seen from Fig. 1, free radicals can be formed
catalyzed by transition metal oxide NPs have recently evolved as via reaction of reactive O−2 with alcohols, leading to the desired
a major research direction of our modern society resulting from products.
A. Akbari et al. / Nano-Structures & Nano-Objects 14 (2018) 19–48 21
Fig. 1. Plausible reaction mechanism for alcohol oxidation over TiO2 nanoparticles [46].
Three different primary cyclohexyl alcohols were oxidized by developed for fabrication of RuO2 /TiO2 nanobelt heterostructures
TiO2 NPs illuminated for 20 h using 450 W medium pressure using a co-precipitation method [55]. Well dispersion of RuO2 NPs
mercury lamp. Photocatalytic oxidation by TiO2 showed different with an average size of 2.4 ± 0.5 nm over the TiO2 nanobelt surface
conversion ratios depending on the type of cyclohexyl alcohol caused the formation of RuO2 /TiO2 which acted as an efficient pho-
used [47]. Suggested mechanism was the formation of electron– tocatalyst in the oxidation of benzyl alcohol under UV and visible
hole pair at the surface of TiO2 NPs followed by oxidation reaction. light irradiation compared with the individual RuO2 NPs and TiO2
Single crystalline rutile TiO2 nanorods were used as an effective nanobelt. Experimental results showed 98, 70 and 55% selectivity
photocatalyst for selective oxidation of benzyl alcohol into ben- for benzyl alcohol oxidation over RuO2 /TiO2 nanobelt heterostruc-
zaldehyde. Rutile TiO2 nanorods were prepared via hydrothermal tures, TiO2 nanobelt, and RuO2 NPs, respectively. This high catalytic
method in which the hydrothermal reaction time affected the activity of RuO2 /TiO2 nanobelt heterostructures could be related to
crystallite size of TiO2 nanorods. For example, the crystallite size the energy band matching between RuO2 and TiO2 as well as the
of as-prepared nanorods was 19.9 nm and 25.5 nm when the ability for separation of photo-generated electron–hole pairs.
hydrothermal reaction time was 4 and 24 h, respectively. By con- Mesoporous materials can be considered as promising com-
trolling the hydrothermal reaction time, it was possible to optimize pounds due to their three-dimensional network and large accessi-
the surface properties of TiO2 nanorods which had a remarkable ble pore surface [56,57]. In this approach, a facile and simple syn-
effect in obtaining higher selective photocatalytic activity [48]. thesis of nanostructured titania using a surfactant-assisted aggre-
The catalytic activity of TiO2 nanorods for selective oxidation of gating assembly of TiO2 NPs was reported [58,59]. The as-prepared
benzyl alcohol was compared with TiO2 NPs. Results showed that TiO2 NPs possessed a high-surface-area but they had a wide band
the former was more active because of its high surface-to-volume gap electron transition (Eg ∼ 3.2 eV). By interconnecting of CdS
ratio which facilitated the interaction, adsorption and desorption quantum dots (ca. 5–6 nm) in the structure of mesoporous TiO2
of organic molecules with the surface. NPs (ca. 8 nm), it was possible to decrease the wide band gap
Selective photocatalytic oxidation of benzyl alcohol and its electron transition to ∼2.5 eV. The CdS–mesoporous TiO2 NPs, as a
derivatives into their carbonyl products (up to 99% in selectivity heterostructured catalyst, showed excellent photocatalytic activity
and conversion) was fully studied over TiO2 NPs under visible-light for the oxidation of various para-substituted aromatic alcohols
by Higashimoto and coworkers [49–51]. From these studies, the into the corresponding carbonyl compounds under UV–visible ir-
authors verified the existence of the interaction between benzylic radiation using molecular oxygen as an oxidant. All alcohols were
alcohol compounds and the surface of TiO2 NPs. On the other hand, converted to the desired carbonyl compounds with up to 99% se-
the interaction of –CH2 OH group or phenyl ring of benzyl alcohol lectivity. The high selectivity could be related to the large internal
with surface hydroxyl groups led to the formation of a surface surface and narrow pore size distribution of NPs in the structure of
complex which induced absorption in the visible region. These the catalyst.
interactions were depicted in Fig. 2. TiO2 NPs were embedded into the three different allotropes
After irradiation with visible light, the surface complex was of carbon, namely Graphene (GR), carbon nanotubes (CNT) and
photo-excited and produced holes (h+ ) which abstracted hydrogen fullerene (C60 ) using a sol−gel process along with hydrothermal
atoms from CH2 OH group of benzyl alcohol. In this process, oxygen post-treatment [60]. Selective photo-oxidation of benzyl alcohol to
molecules not only played a remarkable role as an electron accep- benzaldehyde was employed as a probe reaction to investigate the
tor but also they regenerated the hydroxyl groups on TiO2 surface photocatalytic activity of as-prepared nanocomposites under visi-
and increased the rate of selective oxidation of benzyl alcohol. ble light irradiation. Experimental results showed an efficient cat-
A similar photo-oxidation mechanism was reported for methanol alytic performance for all nanocomposites. Existence of carbon ma-
over rutile TiO2 NPs [52]. terials not only extended the adsorption edge of all TiO2 −carbon
Recently, one dimensional TiO2 nanomaterials or nanobelts nanocomposites to the visible light region, but also increased the
have gained attention as photocatalysts due to their larger surface- lifetime of photo-generated electron−hole pairs. These positive
to-volume ratio and the lower number of grain boundaries [53], effects could be related to their high catalytic activity. The same
but they have some critical drawbacks such as poor visible light authors synthesized TiO2 - GR and TiO2 -CNT nanocomposites by a
utilization, fewer surface active sites and most importantly the simple random integration of solid TiO2 particles with these carbon
high recombination of photo-generated electron–hole pairs which materials [61]. The photocatalytic activity of as-prepared catalysts
remarkably limits their practical applications [54]. Assembling the was tested in the oxidation of various benzylic alcohols.
second phases on the 1D TiO2 nanostructures can solve the afore- In another report, core–shell AgBr@TiO2 NPs were immobi-
mentioned problems. For instance, a simple synthetic protocol was lized onto the surface of graphene oxide (GO) and utilized as a
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- further transfer electrons but also facilitate their trapping by ad-
tive oxidation of benzyl alcohol under visible light irradiation [62]. sorbed oxygen.
The results showed that the AgBr@TiO2 /GO ternary composite In 2013, Wang and colleagues synthesized new single-crystal
exhibited superior photocatalytic activity compared with AgBr, TiO2 with 2D and 3D ordered mesoporous structures and exposed
AgBr@TiO2 , and AgBr/GO. Photoluminescence analysis confirmed (001) facets via solvothermal method using SBA-15 or KIT-6 and
that anchoring AgBr@TiO2 onto GO caused the highest separa- TiOSO4 as hard template and titanium precursor, respectively [63].
tion rate of photo-generated electrons and holes. Photocatalytic The catalytic activity of as-prepared materials was investigated
oxidation mechanism was depicted in Fig. 3. As it could be seen for photo-oxidation of various alcohols under UV-irradiation and
from Fig. 3, GO, with excellent conduction property, not only could the results were compared with polycrystalline TiO2 of a similar
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
Fig. 4. A plausible mechanism of photocatalytic selective oxidation [63]. 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
mesoporous structure. Experimental results revealed that the TiO2 intermediate 4 with side-on peroxide was evidenced by using 18 O
with 3D ordered mesoporous structure exhibited high catalytic labeling and Raman spectroscopy [65].
activity due to its high light harvesting ability as well as reducing The intermediate 4 could be easily decomposed with acids to
the recombination rate between photoelectrons and holes. Authors regenerate the TiO2 based catalyst. On the other hand, protons
proposed a simple reaction mechanism in Fig. 4 by UV light ir- significantly accelerate the disproportionate decomposition of the
radiation, the TiO2 semiconductor produced photoelectrons (e− ) side-on peroxide as depicted in Fig. 6.
and holes (h+ ). Photogenerated holes and electrons are responsible Stronger adsorption of organic compounds on the surface of
for the activation of adsorbed alcohol to produce alcohol cation individual TiO2 NPs would lead to an increase in the amount of
radicals and O2 to form . O− 2 radicals, respectively. At the end, the oxidation products and facilitate the photocatalytic decomposition
. −
O2 radicals reacted with alcohol cation radicals to produce desired of products, followed by a decrease in reaction selectivity. For
product. example, when the photo-oxidation of benzyl alcohol was carried
Two types of TiO2 and SiO2 /TiO2 (7% Si/Ti) were synthesized out over pure TiO2 NPs in water, the benzaldehyde selectivity de-
using a sol–gel method through the hydrolysis of titanium (IV) creased with photo-irradiation time. This indicated that pure TiO2
n-butoxide followed by calcination at 430 ◦ C [64]. The catalytic NPs decomposed the benzaldehyde and formed CO2 as by-product.
activity of as-prepared materials was tested for selective oxidation The suppression of benzaldehyde adsorption onto the TiO2 surface
of benzyl alcohol. Experimental results showed similar selectivity is one possible way to enhance benzaldehyde selectivity. In this
(98%) for both catalysts with 42% and 46% alcohol conversion for approach, partial coating of TiO2 with WO3 NPs was reported by
TiO2 and SiO2 /TiO2 , respectively. Moreover, other experimental Tsukamoto et al. [66]. With this system (WO3 (7.6)/TiO2 ), they
Fig. 5. Proposed reaction mechanism for photo-oxidation of alcohols over TiO2 nanoparticles [64].
(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- mechanism for the title reaction. The reaction mechanism is illus-
cohol from 23% over pure TiO2 NPs to 50%. Fig. 7 shows the reaction trated in Fig. 8.
mechanism on the surface of catalysts. As shown in Fig. 7, the The proposed mechanism was further verified by the addition
overoxidation and decomposition of benzaldehyde occurred on the of 2,6-di-tert-butyl-p-cresol as a radical scavenging agent in this
surface of pure TiO2 NPs. In contrast, WO3 NPs acted as inactive process. When 2,6-di-tert-butyl-p-cresol (0.01 mmol) was added
sites and inhibited the decomposition of benzaldehyde to CO2 . as a radical scavenger, the oxidation was strongly suppressed. The
The oxidation of various organic compounds over TiO2 catalysts same catalytic system was prepared and utilized for the oxidation
is also possible without light irradiation. In one report, various of different sulfides into the corresponding sulfoxides [69].
metal ions were incorporated in the structure of TiO2 NPs using TiO2 nanomaterials with different crystalline structures and
a simple co-precipitation method at room temperature [67]. As- surface morphologies, TiO2 NPs (TiO2 NPs), TiO2 nanotubes (TiO2
prepared metal ion doped TiO2 NPs (M–TiO2 , M = Cr3+ , Mn2+ , NTs) and TiO2 nanofibers (TiO2 NFs) were directly utilized for the
Fe3+ , V5+ , Zn2+ , Ni2+ , Ag+ , Cu2+ and Co2+ ) were utilized for the selective oxidation of hydrocarbon materials under mild, solvent-
oxidation of benzyl alcohol, styrene and toluene without light free conditions [70]. A mean diameter of 1.6 ± 0.4 nm, 60.5 ± 7.0
irradiation in the presence of tert-butyl hydroperoxide (TBHP) as nm and 138.3 ± 1.2 nm was reported for TiO2 NPs, TiO2 NTs
an oxidant. The catalytic behavior of M–TiO2 could be tuned by and TiO2 NFs, respectively using TEM analyses. Catalytic results
changing the metal ion, doping amount, and calcination temper- demonstrated that TiO2 NFs showed slightly better activity com-
pared to the other catalysts tested due to the dominancy of rutile
ature. Experimental results revealed that in the case of styrene
phase in TiO2 NFs.
oxidation, Cu–TiO2 (58 nm) and Co–TiO2 (67 nm) showed higher
A green protocol was developed for the oxidation of 5-(Hydroxy
catalytic activity with 10 and 15 mol% loading of Cu and Co,
methyl)-2-furaldehyde (HMF) to 2,5-furandicarbaldehyde in the
respectively. In addition, Co–TiO2 (20 mol% Co) and Cu–TiO2 (15
presence of home-made anatase, rutile, and brookite TiO2 NPs in
mol% Cu) exhibited the highest catalytic activity in the oxidation
aqueous media [71]. This method provided a fully environmentally-
of benzyl alcohol and toluene toward chlorine-free benzaldehyde,
friendly photocatalytic process which converted the common
respectively.
industrial by-product 5-(Hydroxymethyl)-2-furaldehyde into the
Recently, our research group synthesized a series of vana-
useful corresponding aldehyde. In addition, the five-membered
dium doped TiO2 NPs using titanyl nitrate and ammonium meta- ring HMF, which is less stable compared to other aromatic six-
vanadate as starting materials by a one-pot solution combustion membered ring molecules decomposed to many hydroxylated
method [68]. The oxidation of benzyl alcohol was selected as a species during the photocatalytic oxidation process. Interestingly,
model reaction in order to evaluate catalytic activity of as-prepared experimental results showed the absence of other oxidized species
catalysts. After evaluation of various parameters, maximum activ- in solution throughout this process. Fig. 9 presents the plausible
ity of catalyst (97% conversion and 88% selectivity) was achieved reaction mechanism. As shown in Fig. 9, the rate-determining step
using TiO2 /V15 (V: 0.15 mol%), H2 O2 as an oxidant and methanol as involved the formation of alcoholic group by either a hole (h+ ) or
a solvent. Beside the oxidation of various alcohols, the synthesized a hydroxyl radical, followed by conversion to the aldehyde group.
catalyst showed high catalytic performance for the oxidation of
different substituted olefins. In addition, the catalyst could be 2.2. Group 5 elements (V, Nb and Ta)
recycled 5 times and no significant loss of activity was observed.
It should to be noted that the benzyl alcohol conversion was very 2.2.1. Vanadium oxide nanoparticles
low in the absence of catalyst or H2 O2 by using the TiO2 /V15/H2 O2 Direct use of vanadium oxide NPs in the oxidation reactions
system. This phenomenon encouraged us to propose a free radical is rare. In most cases, vanadium oxide NPs are supported on the
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
pretreatment conditions. In addition, oxygen binding strengths the same authors synthesized MgO particles and used as support
in the vanadia played a crucial role during the oxidation process for the preparation of vanadium oxide NP catalyst via grafting
which was affected by the interaction with support [75]. For in- and impregnation methods [82]. The catalytic performance of as-
stance, vanadia was immobilized onto alumina, zirconia and titania prepared catalysts was evaluated for the liquid-phase oxidation of
supports using impregnation method. In one study, these catalytic cyclohexane. Different parameters such as reaction time, catalyst
systems were utilized in the oxidation of methanol [76]. The effect amount, vanadium loading as well as hydrogen peroxide concen-
of oxygen binding on the catalytic activity of each material was tration were studied. The method of preparation and the amount
investigated by coulometric titration. For all supported vanadia of vanadium loading had remarkable effects on the structure of
catalysts, methanol oxidation was carried out with 90% selectivity prepared catalysts. For example, the oxidation of cyclohexane was
toward formaldehyde. However, for V2 O5 /Al2 O3 the major prod- not considerable for impregnated or grafted MgO-supported vana-
uct was dimethyl ether at the highest temperature. Experimental dium oxide catalysts with low vanadium loading which consisted
results also demonstrated that this reaction followed a Mars–van of isolated VO4 spices. Conversely, new phases like ortho-Mg3 V2 O8 ,
Krevelen mechanism. pyro-Mg2 V2 O7 and meta-MgV2 O6 were formed in the structure of
In another report, the same catalytic systems were used in the catalysts by increasing the amount of vanadium loading, which
selective oxidation of formaldehyde to formic acid [77]. Results
in turn exhibited high conversions ranging from 40 to 67% for the
for formaldehyde oxidation showed that formic acid formation
oxidation of cyclohexane. In all cases explained above, a mixture
occurred on the vanadia species and methyl formate formed
of products was obtained after oxidation of cyclohexane. In order
on the free area of support. Additionally, compared to other
to increase the cyclohexanone/cyclohexanol molar ratio in the
supported-vanadia catalysts, V2 O5 /TiO2 showed the highest activ-
oxidation of cyclohexane, recently Yang and coworkers developed
ity on those surfaces having oligomeric vanadium species. Vana-
a new V2 O5 @TiO2 catalyst by deposition of vanadium spices on
dium and molybdenum oxide particles were supported on the
surface of alumina and titania by Heracleous and coworkers [78] TiO2 [83]. The prepared catalyst exhibited high selective aerobic
and used in the oxidative dehydrogenation (ODH) of ethane and oxidation of cyclohexane to cyclohexanone under simulated solar
propane. Many factors such as the effect of active metal oxide, the light irradiation. The effect of various parameters such as solvent,
effect of support and the effect of alkane were studied in more reaction time, oxygen pressure, amount of vanadium spices de-
details. Results indicated that molybdena catalysts were less active posited on TiO2 was investigated. Among them, different solvents
than vanadia catalysts in the oxidative dehydrogenation of ethane as well as the amount of vanadium spices had remarkable influ-
and propane, irrespective of the support used. Moreover, titania- ence on photocatalytic oxidation of cyclohexane. In another word,
supported catalysts were more active and less selective than those when methylene dichloride/water and n-hexane/water were used
supported on alumina, indicating the great influence of support as the solvents, both conversion and selectivity were low. Con-
on catalytic activity. Beside the above supported metal oxides, the versely, high selectivity (nearly 100%) was obtained using acetoni-
nanometer CeO2 was also used as a support in vanadia catalyst [79]. trile/water as the reaction solvent by volume ratio of 10/1. In the
CeO2 NPs were synthesized using microwave-assisted heating hy- case of amount of vanadium loading, 0.003 to 0.07 g of catalyst
drolysis, then vanadia catalysts with different vanadium loadings (V2 O5 /TiO2 ) was examined. Experimental results demonstrated
were supported on CeO2 NPs via the incipient-wetness impreg- that 0.01 g of catalyst (0.01–V2 O5 /TiO2 ) showed highest conversion
nation method. The catalytic performance of as-prepared catalyst and cyclohexanone/cyclohexanol molar ratio. It is worth to men-
was studied in the oxidation of soot. The amount of vanadium tion that the conversion and ketone/alcohol molar ratio decreased
loaded had a substantial effect on the structure of catalysts. On when the vanadium content of the catalyst was more than 0.01 g
the other hand, isolated mono-vanadate species, poly-vanadate because of the agglomeration of vanadium spices on the surface
species and CeVO4 crystallites were formed at low, medium and of TiO2 . The optimum reaction condition was obtained using ace-
high vanadium loading, respectively. Additionally, the experimen- tonitrile/water as the reaction solvent, 0.01 g of V2 O5 /TiO2 , 2.0 MPa
tal results showed that the poly-vanadate species were more active oxygen pressure and a reaction time of 8 h. The proposed mecha-
than mono-vanadate species and CeVO4 for soot oxidation and the nism is illustrated in Fig. 11. At first, the reactants were adsorbed
nanometer size effect of CeO2 also increased the catalytic activity on the surface of V2 O5 /TiO2 as catalyst. Then the electron (e− ) and
of vanadia catalysts by increasing the contact between the catalyst positive hole (h+ ) pairs were produced under simulated solar light
and soot. irradiation. Subsequently, the generated holes oxidized water and
In the past decades, tremendous efforts have been made in the produced H+ and − OH. At the same time, the generated electrons
selective oxidation of cyclohexane because among the oxidation
reduced V5+ to V4+ which could easily release and transfer the
products, cyclohexanone is an essential intermediate in the pro-
electron to O2 absorbed on the catalyst surface to produce O·− 2 .
duction of nylon-6,6. Research survey showed that vanadium oxide
In order to improve the conversion of cyclohexane oxidation
NPs were used as catalysts in the oxidation of cyclohexane. As men-
reaction, for the first time, a hetero-mixed of vanadium oxide NPs
tioned above, vanadium oxide NPs are supported on the surface of
with WO3 as the catalyst was designed and synthesized [84]. The
other metal oxides in order to improve their catalytic performance.
hetero-mixed catalyst (V2 O5 /WO3 ) was obtained using ethylene
The type of support for oxide materials affected the molecular
structure of the vanadium oxide spices. In one study [80], three dif- glycol and polyvinylpyrrolidone (PVP) as solvent and templating
ferent supports, namely Al2 O3 , SiO2 and TiO2 , were utilized in the agent, respectively, followed by calcination at 500 ◦ C for 4 h. For
synthesis of vanadium oxide based catalysts using wet impregna- comparison, the individual catalysts, V2 O5 and WO3 , were synthe-
tion and grafting as two different synthetic methods. The catalytic sized according to the same procedure. The catalytic activity of all
behavior of as-synthesized catalysts was fully investigated in the as-prepared catalysts was evaluated for the oxidation of cyclohex-
oxidation of cyclohexane. For this purpose, the effect of various ane at room temperature in the presence of H2 O2 . Experimental re-
parameters such as vanadium distribution, reaction time, oxidant sults demonstrated that the conversion efficiency of catalysts was
concentration, catalyst amount and co-catalyst concentration were increased in the order of V2 O5 /WO3 > WO3 > V2 O5 . According to
studied. Experimental results demonstrated that vanadium oxide this finding, it is clear that the combination of two metal oxides had
NPs supported on TiO2 had maximum activity compared to other a synergic influence which facilitated the electron charge transfer
catalysts and gave a mixture of products. Moreover, pyrazine 2- between metals, leading to improved oxidation rates. Controlled
carboxylic acid (PCA) as co-catalyst had a crucial role in the ox- decomposition of H2 O2 into reactive radicals can be assumed as
idation of cyclohexane which accelerated the production of hy- a key point of this reaction. In this approach, the hetero-mixed
droxyl radicals in the presence of hydrogen peroxide [81]. In 2010, V2 O5 /WO3 catalyst enhanced the rate of H2 O2 decomposition. This
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, oxides as MoO2 and MoO3 . Molybdenum oxides (MoOx ) have been
reaction time and catalyst stability had a significant influence on broadly utilized in the field of sensors [85], electrode materials [86]
the conversion and selectivity of cyclohexane oxidation reaction. and recording materials [87]. However the catalytic activity of
Increasing the catalyst amount had a positive effect on reaction these NPs has been reported less than other applications. In most
conversion. For instance, in the case of using 25 mg of catalyst, cases, molybdenum dioxide, MoO2 , has been used as the catalyst
the conversion was 30% while conversion reached 71% at 100 in cracking and reforming of hydrocarbon compounds [88,89].
mg of catalyst. As it can be seen from Fig. 12, the known over- Recently, Bento and coworkers reported novel MoO2 NPs as
oxidation products included adipic acid, 6-hydroxyhexanoic acid efficient catalysts in epoxidation of olefins [90]. Commercial MoO3
and ε -caprolactone can be formed by increasing the reaction time. was used as starting material for the synthesis of tremella-like
HQ
These by-products had dropped the selectivity of the reaction MoO2 NPs in the presence of ethylenediamine and hydro-
remarkably to 63%. quinone as reducing and assisting agents, respectively. The key
point of this study was the use of hydroquinone instead of iron
2.3. Group 6 elements (Cr, Mo and W) oxide [91] which allowed monitoring the sole role of MoO2 in the
epoxidation of olefins. The catalytic application of as-synthesized
2.3.1. Molybdenum oxide nanoparticles MoO2 NPs was tested in the epoxidation of two sets of olefins
Among the known transition metal oxides, molybdenum oxides namely simple olefins and multifunctional olefins. In order to
(MoOx ) have attracted significant research interest due to their find the optimized reaction conditions, different oxygen donors
unique structural characteristics. MoOx has two simple binary tert-butyl hydroperoxide (TBHP) or cumene hydroperoxide (CHP),
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.
Fig. 14. The catalytic redox cycle according to the Mars–van Krevelen reaction mechanism [100].
Unlike Ni-based catalysts, Molybdenum dioxide NPs can be and ZrO2 (MoO3 /ZrO2 , ∼6.5 nm) nanospheres. The stability of the
used as new catalytic materials in the process of Jet-A fuel [97– alkoxide precursors of silica, titania and zirconia can be related
99] directly due to their unique properties such as high oxidation to the differences in particle size. On the other hand, tetraethyl
activity toward Jet-A fuel, high resistance to coking, stability at orthosilicate (TEOS), as silica precursor, was more stable than
high operating temperatures and high sulfur tolerance. In this way, titanium (IV) butoxide and zirconium (IV) butoxide, as precursor of
MoO2 NPs with uniform structures were prepared using molybde- titania and zirconia, respectively. The stability of TEOS decreased
num trioxide as the starting material in a mixture of ethylene glycol the rate of hydrolysis, nucleation as well as the crystal growth,
and water at 180 ◦ C for 12 h [100]. Catalytic activity of as-prepared resulting in the formation of larger particles in the range of 250–
MoO2 NPs was tested for partial oxidation of liquid hydrocar- 300 nm. These hybrid catalysts were fully characterized by various
bons such as n-dodecane at 850 ◦ C and 1 atm. For comparison, physico-chemical techniques. In order to optimize the oxidation
the same oxidation reaction with similar conditions was carried reaction conditions, catalytic activity of the hybrid catalysts was
out by Ni-based catalysts and commercial MoO2 . Experimental evaluated for the epoxidation of cyclooctene in the presence of
results revealed that MoO2 NPs not only had significantly higher TBHP as an oxidant. The experimental results at the optimized
fuel conversion of >90% with a hydrogen yield of >70% but also condition (T = 80 ◦ C, solvent: 1,2-dichloroethane and t = 2 h)
showed a remarkable coking resistance. In contrast, the catalytic showed that MoO3 /SiO2 catalyst gave 90% cyclooctene conversion
performance of Ni-based catalysts and commercial MoO2 was low and 100% selectivity for epoxide product. However, MoO3 /TiO2
due to their low coking resistance which led to deactivation of and MoO3 /ZrO2 showed the same selectivity but their cyclooctene
their surfaces. Moreover, the mechanism of partial oxidation of n- conversion were 37% and 39.5%, respectively. In addition, the scope
dodecane could be explained based on the Mars–van Krevelen re- of the substrate by choosing other alkenes as well as the leaching
action mechanism. The catalytic redox cycle is depicted in Fig. 14. experiment was carried out using MoO3 /SiO2 as the best catalyst.
In this mechanism, adsorption of hydrocarbons occurred on the This catalyst did not show any loss of catalytic activity or leaching
surface of metal oxide NPs, followed by oxidation of the adsorbed even after five runs.
hydrocarbons. Next the insertion of oxygen atoms occurred by re- Generally, olefins with electron-donating groups are more ac-
duction of the metal oxide. This cycle was repeated by re-oxidation tive than olefins with electron-withdrawing groups in epoxidation
of the metal oxide surface, followed by refilling surface oxygen reactions [104]. For instance, the epoxidation of allyl acetate, as a
vacancies by gas-phase oxygen. low active substrate, was carried out by supported MoO3 particles
The activity, selectivity and stability of heterogeneous cata- over SiO2 , TiO2 and Al2 O3 in the presence of TBHP as an oxi-
lysts are affected by many factors such as preparation method, dant [105]. In this research, MoO3 particles supported on Al2 O3 and
the catalyst precursor, reaction temperature and solvents. Among SiO2 were ineffective for epoxidation of allyl acetate. In the case of
them, transition metal oxide precursor is an important factor, MoO3 particles supported on TiO2 , excellent catalytic performance
so the choice of appropriate transition metal precursor can sig- in epoxide selectivity was achieved which could be related to the
nificantly affect the catalyst properties. For example, Arnold and high surface of TiO2 as well as the two-dimensional dispersion of
coworkers [101] synthesized metallosilicates containing molyb- MoO3 . It is worth to highlight that epoxidation of allyl acetate with
denum using two different starting materials, namely Mo(OiPr)5 MoO3 supported on TiO2 in the presence of TBHP was significantly
and MoO2 (acac)2 in the presence of tetraethoxysilane (TEOS) by temperature dependent.
sol–gel process [102]. The catalytic activity of these catalysts was As mentioned before, epoxidation of allyl acetate over
evaluated for epoxidation of cyclooctene in the presence of TBHP MoO3 /Al2 O3 produced a small amount of glycidyl acetate as the
as a green oxidant. The results demonstrated that the prepared- epoxy product. This very low yield can be attributed to the ex-
catalyst using MoO2 (acac)2 as starting material showed high con- istence of acid sites in the structure of MoO3 /Al2 O3 which easily
version (94%) and selectivity (97%) toward the epoxide product. cleaved the epoxy ring of glycidyl acetate during the reaction.
In the case of Mo(OiPr)5 as precursor, 82% conversion with 95% In one study, various types of amines such as pyridine, pyridine
selectivity was achieved. Further, the general scope of these cat- derivatives and aliphatic amines were utilized during the reaction
alysts was tested for epoxidation of various olefins and showed to neutralize the acid sites [106]. Among them, pyridine and pyri-
reusability for three times. However, catalysts showed leaching of dine derivatives showed high selectivity for the epoxidation of allyl
the active species in subsequent runs which limited their applica- acetate toward glycidyl acetate. These amines not only activated
tion as catalyst. MoO3 /Al2 O3 catalyst by coordinating to Mo but also blocked acid
Supported metal NPs can be utilized in the structure of catalysts sites and inhibited the ring-opening of glycidyl acetate.
in order to prevent leaching of the active species. For instance, a In another reported research, the effect of amine additives
reverse micelle microemulsion method was developed for the syn- (pyridine and pyrazole) was comprehensively investigated for the
thesis of very small MoO3 NPs [103]. By this method, as-prepared epoxidation of simple olefins such as styrene and cyclohexene by
MoO3 NPs (1.5–4 nm) were uniformly dispersed and supported MoO3 particles as catalyst [107]. Preliminary results revealed that
onto SiO2 (MoO3 /SiO2 , ∼275 nm), TiO2 (MoO3 /TiO2 , ∼10.5 nm) the epoxidation of styrene by MoO3 particles as catalyst strongly
depended on the amount of amine loading. For example, the olefin supports in the epoxidation of cis-cyclooctene as a probe reaction
conversion dropped from 88% to 76% and 68% by increasing the in the presence of 50% aqueous H2 O2 . Results revealed that the
pyrazole from 0.17 to 0.15 and 0.5 mol%, respectively. In the case epoxidation efficiency was dramatically decreased by employing
of pyridine, the same situation was observed. It seems that the MgO and Montmorillonite K10, whereas the use of TiO2 , CeO2 ,
high concentration of amines improved the activity of Mo (VI) active carbon, or alumina produced moderate activities. In con-
species which caused the oxidative cleavage of the epoxide instead trast, MCM-48 as a support for WO3 resulted in 98% conversion
of protecting the oxirane ring. Gao and coworkers utilized one- and selectivity. The catalytic activity of WO3 -MCM-48 (2–3 nm)
dimensional (1D) molybdenum oxide nanowires as a precur- was also tested in the oxidation of a broad range of substituted
sor for preparation of organic–inorganic materials (Fe–MoOx /PANI sulfides. It is worth mentioning that the sulfide oxidation by WO3 -
nanorods) in the presence of aniline and Fe3+ [108]. In this pro- MCM-48 (2–3 nm) was significantly dependent on the reaction
cedure, Mo3 O10 (C6 H5 NH3 )2 ·2H2 O NWs was used as precursor and conditions. On the other hand, complete conversion of sulfoxides,
reacted with Fe3+ for 2 h. After the addition of aniline, Fe3+ produced using 1.1 equiv of aqueous H2 O2 (50%) for 4 h at 25 ◦ C
ions acted as initiator and polymerized aniline on the surface of in methanol, to sulfones occurred in the presence of 3.0 equiv of
Mo3 O10 (C6 H5 NH3 )2 ·2H2 O NWs. It is worth to mention that using aqueous H2 O2 (50%) at 60 ◦ C for 12 h. In addition, WO3 -MCM-
Mo3 O10 (C6 H5 NH3 )2 ·2H2 O NWs as starting material was vital for 48 (2–3 nm) catalyzed the oxidation of ketones to lactones, the
the preparation of Fe–MoOx /PANI nanorods because the surface Baeyer–Villiger oxidation, with periodic acid in acetonitrile at 60 ◦ C
of Mo3 O10 (C6 H5 NH3 )2 ·2H2 O NWs facilitated material dissolution for 12 h.
and aniline polymerization. Different precursors with various mor- SBA-15 was utilized as another mesoporous silica support in
phologies such as Mo7 O24 (NH4 )6 ·4H2 O, Mo8 O26 (C6 H5 NH3 )4 ·2H2 O the preparation of tungsten oxide based nanocomposites. In one
in bulk form and Mo6 O19 (C6 H5 NH3 )2 needles were used in produc- research, atomic layer deposition (ALD) method was reported for
ing Fe–MoOx /PANI nanostructures. Moreover, the catalytic behav- grafting tungsten oxide species onto mesoporous silica (SBA-15)
ior of these MoOx -based hybrid catalysts was evaluated for epox- surfaces [112]. Well dispersion of tungsten oxide NPs on the sur-
idation of cyclooctene as a probe reaction. Experimental results face of SBA-15 and improvement in thermal stability were the main
showed that Fe–MoOx /PANI nanorods acted as efficient catalysts advantageous of atomic layer deposition (ALD) method. The as-
with 98.8% olefin conversion and 97.2% selectivity toward the prepared WOx -SBA-15 was used as catalyst in the dehydration of
formation of epoxide product. Fe–MoOx/PANI nanorods can be 2-butanol and methanol. Experimental results showed that this
recycled and reused for more than 5 runs without significant loss catalyst exhibited excellent activity compared to WOx -SBA-15 pre-
pared by conventional methods.
in their catalytic activity. In contrast, MoOx/PANI nanorods were
WO3 /SBA-15(OA), WO3 /SBA-15(HP) and WO3 /SBA-15(AM)
deactivated after 2 runs. Therefore, it could be concluded that Fe3+
were synthesized by dissolving tungstic acid, WO3 · H2 O, in aque-
ions improved stability of the catalyst via formation of insoluble
ous solution of oxalic acid, hydrogen peroxide and ammonium
ferric molybdate [109].
paratungstate, respectively, using the conventional incipient wet-
Recently, an efficient magnetic γ -Fe2 O3 @C@MoO3 based cata-
ness impregnation method [113]. The catalytic performance of as-
lyst with core–shell structure was produced and used for epox-
prepared nanomaterials was studied for selective oxidation of cy-
idation of cyclooctene with tBuOOH as an oxidant [110]. In this
clopentene (CPE) to glutaraldehyde (GA). The dispersion or aggre-
method, glucose as the carbon source was used for the coating
gation of tungsten oxide NPs onto the supports were analyzed by
of magnetic NPs which prevented their aggregation and stabilized
transmission electron microscopy (TEM) and X-ray powder diffrac-
the NPs. Modification of as-prepared material with poly (dial-
tion (XRD). According to these analyses, the dispersion of tungsten
lyldimethylammonium chloride) (PDDA) facilitated the adsorption
species obeyed the order WO3 /SBA-15(OA) > WO3 /SBA-15(HP) >
of Mo7 O624− ions on the surface of magnetic microspheres. Finally,
WO3 /SBA 15(AM). It is worth highlighting that the title reaction
multifunctional hybrid material, γ -Fe2 O3 @C@MoO3 , was obtained
was carried out with the same order. On the other hand, WO3 /SBA-
by a hydrothermal process at 180 ◦ C for 16 h. The catalytic func- 15(OA) and WO3 /SBA-15(HP) catalysts exhibited perfect catalytic
tion of as-prepared material showed 100% conversion and 99% behavior as compared with WO3 /SBA-15(AM) and homogeneous
selectivity toward the formation of epoxide product. In addition, tungstic acid catalysts for the title reaction not only in terms of
the catalyst showed high catalytic performance even after 9 runs conversion of CPE but also in terms of selectivity toward GA.
with 94.7% conversion and 99.6% selectivity. Fig. 15 illustrates the In another report, an efficient and stable WOx -SBA-15 nano-
reaction mechanism of epoxidation which is based on the FT-IR and composite catalyst was obtained using the hydrothermal method
XPS measurements. [114]. In this protocol, tetraethylorthosilicate (TEOS), aqueous
This mechanism suggests that two transition states, namely sodium tungstate solution (NaWO4 ·2H2 O, 0.5 M) and a polyethy-
olefin complex and Mo-alkyl peroxide, were substantial for the lene oxide-block-polypropylene oxide-block-polyethylene oxide
high activity of catalyst. triblock copolymer were used as silica source, tungsten source
and structure-directing agent, respectively. This nanocomposite
2.3.2. Tungsten oxide nanoparticles catalyst showed high activity in selective oxidation of sulfides to
It is well established that immobilization of well-dispersed sulfoxides in the presence of 70% aq. tert-butyl hydrogen peroxide
nanoscopic materials in high-surface area supports can enhance at room temperature. In the selective oxidation of allyl phenyl
their catalytic activity as well as product selectivity. In this regard, sulfide to corresponding sulfoxides, experimental results demon-
tungsten oxide NPs were immobilized on various supports such strated that overoxidation to the sulfone or epoxidation of the
as SBA-15, MCM-48 and MCF and then used in a wide variety of double bond did not occur. Successful oxidation of various sulfur
oxidation reactions. compounds with high selectivity and conversion over this catalyst
For instance, tungsten (VI) oxide NPs were uniformly dispersed could be related to the large pore diameter and low surface acidity
on the surface of an ordered mesoporous support (MCM-48) [111]. of WOx -SBA-15.
The as-prepared WO3 -MCM-48 (2–3 nm) catalyst was utilized Nano-supported tungsten oxide SBA-15 materials have lim-
as an outstanding heterogeneous catalyst for the oxidation of itations such as low thermal stability, structure collapse after
different substrates such as sulfides, olefins and cyclic ketones high-temperature calcinations, and inherent leaching. In order to
in the presence of peracetic acid or hydrogen peroxide. In the overcome these obstacles, mesocellular silica foams (MCF) were
aforementioned research, the influence of the nature of supporting prepared and used as a new support in the preparation of sup-
materials and their size were evaluated by using different kind of ported tungsten oxide NPs [115]. In this work, WO3 -MCF catalyst
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 Cu, Ag, Zn, Cd, Ga, and In) as additives which were supported on
M) aqueous solution to the mixture of Pluronic P123 triblock SnO2 [117]. The catalytic performance of W–X/SnO2 significantly
polymer, 1,3,5-trimethylbenzene and Si(OC2 H5 )4 (TEOS), followed depended on the additives (X). As a probe reaction, the epoxidation
by calcination at 500 ◦ C in air for 8 h [116]. After calcination, of 1-hexene was studied over W–X/SnO2 catalyst in the presence
as-prepared material was treated by ammonium acetate (AMA) of 60% aqueous H2 O2 . Results showed that the highest yield (93%)
to rapidly balance the percentage of tungsten between the solu- with a 95% selectivity for 1,2-epoxyhexane could be obtained over
tion and catalyst. The catalytic activity of these materials were W–Zn/SnO2 . In contrast, when X was from groups 10–14 elements,
evaluated for the epoxidation of cycloocta-1,5-diene (COD) and catalyst activity was moderate and when X was from groups 1–
their performances were compared with other mesoporous silica 3, the catalyst was not active. Dimethyl carbonate (DMC) was
supported tungsten oxide catalysts (WO3 -SBA-15 and WO3 -MCM- selected as the best solvent for the title reaction. The catalytic
41). Characterization of the materials demonstrated the formation activity of W–Zn/SnO2 system for the oxidation of various amines,
of ultra-large pores and unique 3-D cell-window structure (18– silanes, sulfides and alkenes into the corresponding N-oxides,
24 nm) in WO3 -MCF material. Moreover, AMA treatment removed silanols, sulfoxides and epoxides was evaluated in the presence of
loosely bonded tungsten species from WO3 -MCF surface. With this H2 O2 as a green oxidant. Experimental results demonstrated that
treatment, only single-site tetrahedra (WO4 ) species remained on polytungstates with dioxo groups in W–Zn/SnO2 had a critical role
the surface which enhanced the catalytic activity of WO3 -MCF. The in the oxidation process.
oxidation reaction of COD is depicted in Fig. 16 showing the main-
product and by-products. 2.4. Group 7 elements (Mn, Tc and Re)
The effect of different parameters such as the type of support,
tungsten oxide loading, AMA-treatment cycles, calcination tem- 2.4.1. Manganese oxide nanoparticles
perature as well as the reaction time were fully investigated for 2.4.1.1. Alcohol oxidation. Recently, extensive research has been
the epoxidation of COD in the presence of H2 O2 . All experimental devoted to aerobic oxidation of alcohols by manganese oxide NPs.
results demonstrated that the catalytic activity of WO3 -MCF mate- These studies showed significant catalytic activity and selectivity
rials for the title reaction was higher than WO3 -SBA-15 and WO3 - even up to 100% [118]. In general, catalytic performance of the NPs
MCM-41. depended on particle size. On the other hand, smaller particle sizes
In 2011, Kamata and coworkers reported new catalysts based led to higher activity in oxidation reactions. In contrast, NPs were
on the combination of tungsten with various metals (W–X/SnO2 , X not stable and prone to aggregate formation with decreasing par-
= Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Y, La, Ce, Pr, Sm, Eu, Dy, Yb, Ni, ticle size which reduced their stability and catalytic activity [119].
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 and molecular oxygen with various solvents were tested at room
onto solid supports. For instance, Xiang and coworkers developed temperature. 100% conversion and 85% selectivity were obtained
a new route by decoration of MnO2 NPs on Graphene oxide. In in acetonitrile and in the presence of O2 as an oxidant.
this work, MnO2 /GO composites exhibited a high performance in Recently, several promoters with synergistic effects have been
the oxidation of benzyl alcohol to benzaldehyde in the presence developed to increase the catalytic activity of MnOx systems in
of air as an oxidant [120]. Overall schematic representation of this the oxidation of benzyl alcohol. For example, in one report, Ce and
protocol is depicted in Fig. 17. Fe were added on the structure of MnOx materials and the redox
As shown in Fig. 17, MnO2 /GO composite was synthesized by a properties as well as the reactivity of MnOx system as a catalyst in
simple in-situ growth method using MnSO4 and GO as the source of liquid phase were rigorously studied for the selective oxidation of
Mn ions and support, respectively. Well dispersed ultrafine MnO2 benzyl alcohol [123].
NPs (ca. 3 nm) could be synthesized by the simple in-situ growth. Aerobic oxidation of 5-Hydroxymethylfurfural (HMF) to 2,5-
The key point is the combination of GO with MnO2 which has a syn- diformylfuran (DFF) is one of the most important reactions in or-
ergistic effect on catalytic activity of MnO2 /GO composites. 96.8% ganic transformations. DFF is known as a versatile intermediate for
benzyl alcohol conversion and 100% benzaldehyde selectivity was the synthesis of many important products. Selective oxidation of
obtained over MnO2 /GO (10/100) catalyst within 3 h under 383 K. HMF to DFF is difficult because of the existence of the more reactive
Our research group prepared MnO2 NPs via a simple and
α, β -unsaturated aldehyde group in HMF. In this regard, different
catalytic systems have been tested for selective oxidation of HMF
novel protocol and used for the oxidation of benzylic alcohols
to DFF. Liu and coworker used a cryptomelane-type manganese
to corresponding aldehydes [121]. In our approach, MnO2 NPs
oxide octahedral molecular sieve with a (2 × 2, 4.6 Å × 4.6 Å) tunnel
were obtained in-situ by the reaction of Mn (II) (tptz)-Cl2 (H2 O)
size (OMS-2) in order to catalyze the oxidation of HMF to DFF with
as a mononuclear complex with oxone where tptz and oxone
a high yield of 97.2% at 383 K and 0.5 MPa O2 in DMF [124]. In
are 2,4,6-tris(2-pyridyl)-1,3,5-triazine ligand and 2KHSO5 ·KHSO4 ·
this study, catalytic activity of other MnO2 catalysts with different
K2 SO4 oxidant, respectively. EPR spectroscopy enabled us to pro- structures and morphologies were also tested. Results showed that
pose a mechanism for the formation of MnO2 NPs from Mn (II) OMS-2 has high activity and selectivity due to its tunnel structure
(tptz)-Cl2 (H2 O). Based on experimental results, we concluded that as well as its ability for reduction and oxidation.
III,IV
the accumulation of mononuclear complexes such as Mn2 oc- Versatility of OMS-2 as a green and efficient catalyst was
curred before the formation of MnO2 NPs. Existence of the ligand demonstrated by the oxidative amidation of primary alcohols or
around Mn oxide particles not only played an important role in the aldehydes to primary amides in aqueous ammonia. In one com-
formation of NPs but also increased the activity and selectivity of prehensive study, Mizuno and colleagues utilized OMS-2 and other
MnO2 NPs toward alcohol oxidation. manganese-based catalysts with different structures to oxidize
In another work, we synthesized nanolayered Mn oxides in the various kinds of structurally diverse primary alcohols or aldehy-
presence of CaCl2 ·4H2 O and used them as catalysts for alcohol des into the corresponding primary amides in moderate to high
oxidation under ambient condition [122]. High surface area, ther- yields [125]. A four-step mechanism was proposed for the OMS-2-
modynamic stability, and low surface enthalpy are some of the catalyzed amidation. As shown in Fig. 18, the steps include: (i) aer-
advantages of these layered structures. Catalytic performance of obic oxidative dehydrogenation of primary alcohols to aldehydes
Ca0.16 MnO2 ·2H2 O was examined in the oxidation of benzyl alcohol (step 1), (ii) dehydrative condensation of the aldehydes and ammo-
as a model reaction. Different oxidants such as TBHP, H2 O2 , NaClO nia to aldimines via hemiaminal intermediates (step 2), (iii) aerobic
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. Fig. 19. Presentation of proposed mechanism for olefin epoxidation over man-
ganese oxide [129].
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 Four different kind of manganese oxides (MnO, MnO2 , Mn2 O3
materials [127,128]. and Mn3 O4 ) were synthesized via solid-state reaction procedures
Recently, we developed a simple, safe and economical method and used as a catalytic system in epoxidation of various olefins
to prepare nano-sized particles of manganese oxide by decompo- in the presence of 30% H2 O2 as an oxidant in bicarbonate solu-
sition of an aqueous solution of manganese nitrate at 100 ◦ C [129]. tion [131]. Comparison of catalytic activity of these manganese
The synthesized metal oxide NPs were characterized using FT-IR, oxides revealed that MnO has superior activity for the conversion
SEM, TEM and XRD. We also investigated the catalytic performance of styrene to obtain 92.4% selectivity of the corresponding epoxide.
of manganese oxide NPs in epoxidation of various olefins in the Furthermore, these findings confirmed that manganese must be
presence of H2 O2 . Results showed that the nano-catalyst has ex- in its lowest oxidation state, implying that the oxidation state
of manganese has a substantial role in determining the catalytic
cellent activity toward epoxidation of aromatic olefins but mild
activity of the manganese oxide species. In addition, bicarbonate
activity for epoxidation of non-aromatic olefins. Reusability of the
solution has a critical role in epoxidation because no product was
catalyst was also tested which was 86% conversion after six runs.
obtained in the absence of bicarbonate solution. According to the
The proposed mechanism for epoxidation of olefins by manganese
proposed reaction mechanism in Fig. 20, the nucleophilicity of
oxide NPs is schematically depicted in Fig. 19. HCO− 4 ions are more than H2 O2 and subsequently act as an efficient
We have synthesized nano-layered manganese oxides which oxidant in this system.
are embedded in calcium (II), zinc (II) or aluminum (III) and used In this mechanism, coordination of HCO− 2+
4 with Mn on the
as a catalytic system for epoxidation of various olefins using anhy- surface of catalyst can produce intermediate (I). This intermediate
drous tert-butyl hydroperoxide (TBHP) as the oxidation reagent. possesses active atomic [O] which can be transferred to the C–
The production of these metal oxide NPs can be easily scaled up C bond of alkene molecule, forming the epoxide product. Mn2+
via simple, cheap and environmentally friendly processes without is produced by quick decomposition of intermediate (II) on the
using any toxic organic materials [130]. surface of catalyst.
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
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 prevent their aggregation as well as for ease of post-modification.
by the preparation method, their morphology and tunnel struc- The application of ‘‘free’’ iron oxide NPs as a catalyst is rare.
tures [144,145]. In one report, α -, β -, γ - and δ -MnO2 with different In one report, bulk α -F2 O3 , bulk γ -F2 O3 , nano-γ -F2 O3 (particle
crystal structures were synthesized by hydrothermal method and size of 20–50 nm) and nano-γ -F2 O3 (particles size of 3–5 nm)
used as catalysts for oxidation of formaldehyde [146]. Experimen- were utilized in the oxidation of various alcohols and olefins to
tal results showed that δ -MnO2 had the best catalytic activity with corresponding carbonyl products [148]. The efficiency of these
100% formaldehyde conversion at 80 ◦ C compared to other Mn catalysts was studied in selective oxidation of benzyl alcohol as a
oxides. High catalytic activity of δ -MnO2 originated from its special probe molecule in the presence of 33% H2 O2 at 75 ◦ C. The particle
2D layer tunnel structure as well as the highest content of lattice size of as-used iron oxide NPs had a substantial effect on conver-
oxygen species on the catalyst surface. sion and selectivity of benzyl alcohol oxidation. The conversion
Solvent-free aerobic oxidation of hydrocarbons was carried out and selectivity increased in the order of nano-γ -F2 O3 (3–5 nm)
in the presence of Mn3 O4 NPs [147]. These NPs were successfully >nano-γ -F2 O3 (20–50 nm) > bulk α -F2 O3 >bulk γ -F2 O3 . The high-
synthesized via a facile one-pot etherification at low temperature. est catalytic activity belonged to nano-γ -F2 O3 (3–5 nm) with 85%
Controlling the size of the synthesized Mn3 O4 NPs by changing the conversion and 35% selectivity. Furthermore, unsupported ‘‘free’’
reaction temperature was the key point of this study. On the other nano-γ -F2 O3 was used as an efficient catalyst in the oxidation of
hand, when the reaction temperature was 90 and 120 ◦ C, uniform styrene and its derivatives to aldehydes using H2 O2 as a green
and well-dispersed Mn3 O4 NPs with average size of 10 nm was oxidant. The use of ‘‘free’’ nano-F2 O3 in place of immobilized nano-
obtained. By increasing the reaction temperature to 150 ◦ C, the NP F2 O3 was the significance of these results.
size increased to an average size of 15 nm. In order to investigate Ultrasound-activated reaction was employed by Askarinejad
the catalytic capability of as-prepared Mn3 O4 NPs, oxidation of and colleagues for the synthesis of α -F2 O3 (hematite) NPs [149].
ethylbenzene was selected as a model reaction. Compared to other In this method, the uniform and crystalline α -F2 O3 (hematite) NPs
catalysts such as commercial Mn3 O4 and manganese acetate, the were synthesized via ultrasound irradiation of Fe(OAc)2 alkaline
as-prepared Mn3 O4 NPs showed 50% conversion and 81% ace- solution followed by calcination at 900 ◦ C, as shown in Fig. 23.
tophenone selectivity in solvent-free condition at 130 ◦ C for 8 h. 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
2.5. Group 8 elements (Fe, Ru and Os) 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
2.5.1. Iron oxide nanoparticles 50 ◦ C were selected as the optimum reaction conditions. For nano-
In recent years, considerable effort has been devoted to the sized α -Fe2 O3 , 95% conversion of methyl phenyl sulfide and 88%
preparation and application of iron oxide NPs due to their unique selectivity toward sulfoxide were obtained while α -Fe2 O3 in bulk
properties such as low toxicity, good dispersibility, and easy sep- gave 54% conversion for this reaction. These results indicated that
aration using an external magnetite. Compared to other transition size had a remarkable influence on catalytic performances.
metal oxides as catalysts and from the view point of catalytic Recently, ferric hydroxide, Fe(OH)3 , was prepared by a homo-
application, magnetic recoverability can be a unique advantage geneous chemical precipitation method and utilized as a precursor
which eliminates catalyst separation by centrifugation or filtration in the preparation of α -F2 O3 (hematite) NPs by calcination in the
after completion of the reaction. In most cases, iron oxide NPs presence of polyethylene glycol of different molecular weights
are shielded by capping agents, especially silica based agents, to (PEG 400 and PEG 4000) [150]. The key advantage of this method
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
Fig. 24. Overall schematic reaction for oxidation of alcohols and sulfides by
polyvinyl alcohol (PVA) as a biocompatible and nontoxic polymer
Fe2 O3 /SBA-15 catalyst [152].
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 oxide NPs [153]. Characterization of as-prepared nanomaterials
mixed and dispersed in PVA solution in alkaline media. Next, the with XRD and other techniques demonstrated presence of the
brown gel was dried in an open beaker in a water bath at 85 ◦ C. hematite phase (Fe2 O3 , JCPDS card 39-0664) in the structure of the
Finally, two types of magnetic iron oxide NPs were obtained by catalysts. The activity of these catalysts was also investigated in the
thermolyzing a PVA–Fe(OH)3 gel matrix at 400, 500, 600, and oxidation reaction of alcohols toward the corresponding carbonyl
700 ◦ C. The calcination temperature of PVA based gels had a compounds under inert condition. Experimental results showed
significant effect on the nature of iron oxide magnetic products. that both catalysts work efficiently in the oxidation of benzylic
Heating the gel at 700 ◦ C resulted in the formation of α -F2 O3 NPs alcohols with either electron-donating or electron-withdrawing
whereas heating the gel to 400, 500, 600 ◦ C lead to the formation substituents as well as in less sterically-favored positions within
of γ -F2 O3 NPs as the sole product. Selective epoxidation of styrene the aromatic ring with over 90% efficiency. Unfortunately, conver-
was carried out in the presence of α -F2 O3 NPs in aqueous solution sions were relatively low in the case of linear alcohols which were
of TBHP as the oxidant. Experimental results showed that styrene attributed to acid-catalyzed intermolecular etherification between
conversion and selectivity increased by increasing the reaction the two linear alcohol molecules which was in direct competition
time. After 6 h of reaction, reaction conversion and selectivity for with the oxidation reaction.
epoxide reached 73% and 77%, respectively. Wang and coworkers prepared Fex O supported on SBA-15 and
Different types of mesoporous silica materials can be used used it for oxidation of propylene in the presence of nitrous ox-
as a support for stabilization of metal NPs. Among them, SBA- ide [154]. They successfully altered the reaction pathway from
15 has gained significant attention due to its high surface area, production of acrolein to propylene oxide. Conversely, the main
thermal stability, and large pore diameter. Highly active F2 O3 product was acrolein when the oxidation of propylene was carried
NPs embedded in SBA-15 were synthesized by the hydrothermal out with Fex O/SBA-15. Modification of Fex O/SBA-15 with alkaline
method [152]. As shown in Fig. 24, the as-prepared Fe2 O3 /SBA-15 earth metal salts led only to the formation of propylene oxide
showed excellent catalytic performance in oxidation of alcohols (PO) [155], as depicted in the reaction pathway of Fig. 25.
and sulfides. The nature of the alkali metal ion had a direct influence on
In this study, the effect of many factors such as catalyst loading, PO selectivity, conversion and turnover frequency (TOF). Differ-
reaction temperature, type of oxidant, solvent and the reusability ent alkali metal ions were tested for the oxidation of propy-
of catalyst on the oxidation of benzyl alcohol were investigated lene by Fex O/SBA-15 catalyst. It was demonstrated that PO se-
as a model substrate toward the corresponding products. As a lectivity and yield increased in the following order: KCl > NaCl >
result, 20 mg of Fe2 O3 /SBA-15 were used with H2 O2 in water at RbCl > CsCl > LiCl. Experimental results showed that the product
80 ◦ C for 3.5 h in the oxidation of alcohol. Under optimum reaction selectivity in the oxidation of propylene over KCl–Fex O/SBA-15
conditions, Fe2 O3 /SBA-15 showed highest catalytic activity with was 76, 1.8 and 1.1% toward PO, acrolein and allyl alcohol, respec-
95% conversion of benzyl alcohol to benzaldehyde. Fe2 O3 /SBA-15 tively. KCl as an efficient modifier played a key role via interaction
exhibited an excellent catalytic performance in the oxidation sul- with iron species in the oxidation of propylene toward PO. In
fides to sulfoxides without further oxidation to the sulfone under other words, this interaction not only decreased the lattice oxygen
the same reaction condition. associated with iron species, but also eliminated the surface acidity
As alternative supports, two types of aluminosilicates namely originated from iron species. Most importantly, KCl altered the
Al-MCM-41 and Al-SBA-15 were used as support to stabilize iron local coordination of iron structure.
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 As can be seen in Fig. 26, individual Fe2 O3 NPs had maximum
found to be a good candidate because of its high chemical stability, interaction with TiO2 NPs. On the other hand, the volume available
strong metal–support interaction, and acid–base property [156]. for interaction (confinement effect) between these NPs was higher
Recently, TiO2 anatase with three different morphologies namely, than TiO2 -NTs and TiO2 -NFs with Fe2 O3 NPs. Moreover, the TiO2 -
nanoparticles (NP), nanofibers (NF) and nanotubes (NT) were pre- NP support not only increased the specific surface area but also
pared and used as supports with Fe2 O3 NPs (1, 3, 5 and 7 mol% increased the number of Lewis acid sites.
Fe). The catalytic performance of as-prepared iron oxide supported Soni and coworkers utilized zirconium oxide (ZrO2 ) NPs as a
TiO2 nanomaterials was tested for liquid phase oxidation of ben- stable support in the preparation of iron oxide based catalysts
zyl alcohol under a variety of reaction conditions. The optimum (Fe2 O3 –ZrO2 ) [157]. In the aforementioned study, the modified
reaction condition was 0.05 g of catalyst in the presence of 60 sol–gel method with citric acid and the co-precipitation method
mmol H2 O2 at 100 ◦ C for 6 h was which resulted in highest conver- were employed in order to synthesize nanostructured Fe2 O3 –
sion and selectivity toward benzaldehyde. All synthesized Fe2 O3 – ZrO2 (18 nm) and bulk Fe2 O3 –ZrO2 (120 nm)catalysts, respectively.
TiO2 nanomaterials showed catalytic activity in the oxidation of The catalytic potential of as-prepared catalysts was investigated
benzyl alcohol with different efficiencies. Among them, iron oxide for the oxidation of dimethyl sulfide (DMS) in the presence of
supported on TiO2 NPs showed the best performance. It is worth ozone. Citric acid as a chelating agent played a critical role in the
mentioning that the interaction between Fe2 O3 NPs and TiO2 -NPs, preparation of nanostructured Fe2 O3 –ZrO2 with the size of 18 nm
NTs, NFs played a significant role on their application as catalysts, via the modified sol–gel method. Experimental results revealed
as depicted in Fig. 26. that the rate of DMS adsorption and oxidation over nanostructured
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 Fig. 28. Plausible reaction pathway for the formation of MFe2 O4 [163].
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 simple co-precipitation method in alkaline medium [161]. The as-
had a crucial role as solvent and reducing agent, respectively. In prepared Fe3 O4 MNPs were utilized as a magnetically recoverable
this process, hydrazine hydrate released N2 and NH3 by reducing catalyst in oxidation of various primary and secondary benzylic
Fe3+ into Fe2+ leading to the reaction of NH3 with water and the and aliphatic alcohols into their corresponding carbonyl products
production of hydroxyl ions. Further reaction of Fe3+ and Fe2+ with in aqueous medium with hydrogen peroxide as an oxidant at
hydroxyl ions under hydrothermal condition resulted in the forma- 50 ◦ C. Under optimized condition, all reactions afforded the desired
tion of Fe3 O4 particles. The viscosity of EG as well as insolubility products in good to excellent yields. In addition, the experiments
of N2 in EG lead to the formation of gas bubbles which acted as a on reusability of catalysts showed no loss in catalytic activity even
template in the formation of porous Fe3 O4 particles. Epoxidation after four runs.
of styrene toward styrene oxide as a model reaction was carried Recently, nanocrystalline spinel ferrites with a composition of
out in the presence of porous Fe3 O4 and Au/L–Fe3 O4 . Experimental MFe2 O4 (M = Ni and Co) were synthesized by Paul and cowork-
results showed 43.1% conversion and 74.1% selectivity to styrene ers. A simple and versatile hydrothermal method was utilized to
oxide within 13 h in acetonitrile in the case of porous Fe3 O4 as synthesize MFe2 O4 by heating the mixed hydroxide (M(OH)2 +
catalyst. In contrary, immobilization of Au onto the porous Fe3 O4 Fe(OH)3 ) precursor obtained by a co-precipitation method
particles enhanced catalytic activity of the catalyst by 76.1% and [162,163]. In order to produce small NPs with narrow size dis-
70.1% for conversion and selectivity, respectively. tributions, the investigators used PEG 4000 and tributylamine as
In one study, Wang and coworkers compared the catalytic per- surfactant and hydroxylating agent, respectively. Employing this
formance of three different iron oxides, i.e. Fe3 O4 , FeO and Fe2 O3 , strategy led to the synthesis of NiFe2 O4 with size of 2–10 nm and
in epoxidation of alkenes [159]. They selected the epoxidation of CoFe2 O4 with size of 2–30 nm. A plausible reaction pathway for the
styrene as a model reaction in the presence of molecular oxygen formation of MFe2 O4 (M = Ni and Co) is illustrated in Fig. 28.
as an oxidant. The preliminary findings showed that Fe3 O4 had The catalytic potential of as-synthesized nanomaterials was
highest efficiency with 38% conversion and 56.5% selectivity. FeO evaluated in the oxidation of various alcohols to aldehydes by
had lower specific surface area and showed a lower activity. Fe2 O3 periodic acid.
had similar specific surface area to Fe3 O4 but it was almost inactive
for the reaction. Existence of Fe2+ in the crystalline structure of 2.6. Group 9 elements (Co, Rh and Ir)
Fe3 O4 was assumed to be the reason for higher activity of Fe3 O4 in
epoxidation of styrene in the presence of O2 . 2.6.1. Cobalt oxide nanoparticles
Ferrous ammonium sulfate (NH4 )2 Fe(SO4 )2 and ferric chloride Cobalt oxide NPs have received significant attention due to their
(FeCl3 ) were used as starting materials in the preparation of applications in many different fields such as electrochemical, gas
Fe3 O4 magnetic nanoparticles (MNPs) via simple co-precipitation sensing and catalysis [164–168]. The size and morphology of metal
method in alkaline medium [160]. The as-synthesized Fe3 O4 MNPs oxide NPs are important to their catalytic activity in oxidation re-
were utilized as catalyst in the oxidation of benzoin to benzyl (up actions. There is a strong correlation between the aforementioned
to 90%) as a probe reaction in toluene at 80 ◦ C, as shown in Fig. 27. factors and activity as well as selectivity of these catalysts.
This optimum reaction condition was achieved after evaluation In this regard, three different cobalt oxide nano-catalysts were
of different parameters such as temperature, solvent, oxidant, and synthesized using a simple hydrothermal process [169]. Polyhe-
reaction time. It is important to mention that Fe3 O4 MNPs simulta- dral oligomeric silsesquioxane (POSS) bearing 16 carboxylic acid
neously acted as a heterogeneous catalyst and as an oxidant in the groups which can easily couple to the metal carbonyl groups, was
oxidation of benzoin. The oxidation of other alcoholic substrates used as a silica support for cobalt oxide catalyst. Compared to
was also tested by Fe3 O4 MNPs. Experimental results demon- other silica supports, advantages of POSS NPs [170] include well-
strated that Fe3 O4 MNPs could oxidize efficiently nitro alcohols to dispersion of cobalt oxide NPs in the structure of POSS based
nitro ketones. However, there was no reaction with amino alcohols support which increased catalytic activity of cobalt oxide during
in the presence of MNP at 80 ◦ C. the hydrothermal process and protection of cobalt oxide from
In another report, Sadri and colleagues used the FeCl2 ·4H2 O and sintering by POSS. Moreover, POSS supported cobalt oxide cata-
FeCl3 ·6H2 O as precursors for the preparation of Fe3 O4 MNPs using lysts have a uniform morphology with a narrow size distribution
after calcination. The calcination was carried out in three different the formation of CuO particles with a cluster shape. In contrary,
temperatures of 150, 550 and 650 ◦ C which led to labeling the commercial CuO is a bulk material and has no specific morphol-
catalyst as Co3 O4 -150, Co3 O4 -550 and Co3 O4 -650, respectively. The ogy. Moreover, the above research tested the catalytic activity of
catalytic performance of these catalysts with different nanocrys- these CuO particles with different morphologies in epoxidation of
talline structures was tested in the oxidation reaction of styrene norbornene in the presence of t-butyl hydroperoxide as an oxidant.
in the presence of H2 O2 as a green oxidant. Experimental results Because of their uniform and organized shapes, the urchin-like CuO
demonstrated that morphology and size of cobalt oxide NPs can NPs showed excellent catalytic performance with 89.5% conversion
be controlled by tuning the synthetic parameters which resulted and 100% selectivity compared with other CuO particles. Trans-
in Co3 O4 -550 having extraordinary activity and high selectivity stilbene and cis-cyclooctene were also successfully converted to
toward styrene oxide. the corresponding epoxide products with moderate conversion
In 2014, Beller and coworkers developed a novel cobalt oxide and high selectivity in the presence of urchin-like CuO NPs as an
based heterogeneous catalyst [171]. Wet impregnation method efficient catalyst.
was used in the presence of cobalt (II) acetate and different types As mentioned above, the preparation method and type of cop-
of ligands bearing nitrogen atoms on Vulcan XC72R followed by per precursor are two important factors which influence the cop-
pyrolysis at 800 ◦ C. This system showed excellent oxidation per- per oxides microstructure as well as their catalytic activity. In
formance in epoxidation of many different types of olefins such as this regard, microwave-assisted hydrothermal method was em-
renewable olefins as well as cholesterol and vitamin derivatives ployed in order to synthesize CuO NPs with different shapes [185].
with excellent chemoselectivity for the respective epoxides. In this study, urchin-like CuO NPs (CuO-1) were formed under
Synthesis of Co3 O4 nanocrystals with narrow size distribution is microwave radiation for 30 min when Cu(OAc)2 /urea was used
a challenging issue due to their fast precipitation and the formation as starting material. Interestingly, rod-like nanoparticles (CuO-2)
of particle agglomerates with unusual shape in synthetic process. which self-assembled into flower-like structures were formed by
In this regard, a new efficient precipitation method was developed using Cu(NO3 )2 /urea as the precursor. The mechanism of formation
for preparing cobalt oxide nanocrystals using cobalt nitrate as the of these copper oxides was studied by XRD and SEM techniques
precursor in the presence of N-Cetyl-N,N,N-trimethyl ammonium and catalytic activity of these two copper oxides were investigated
bromide (CTAB) and in-situ generated triethylamine salt [172]. in epoxidation of olefins in the presence of TBHP. Styrene was
Inorganic–organic layered particle model was used for the inter- selected as the model reaction and its epoxidation was studied
pretation of nanocrystal formation. According to this model, the in detail during 24 h by CuO-1 and CuO-2. Experimental results
showed that 28% selectivity was obtained toward styrene oxide
organic cations which originated from CTAB and in-situ generated
after 1 h in the case of CuO-1. In contrast, selectivity was almost
triethylamine salt were adsorbed on the polar surface of metal
zero as CuO-2 was used as the catalyst for 1 h indicating that CuO-
oxide particles which separated the NPs from each other by de-
1 with its larger surface area had higher catalytic activity in the
creasing van der Waals interactions between the nanoparticles.
initial stage of the reaction. After 24 h of reaction, styrene was
The catalytic activity of these cobalt oxide NPs was compared
completely oxidized using both CuO-1 and CuO-2 catalysts. After
with the bulk cobalt catalyst for oxidation of cyclohexane in the
8 h of reaction, the conversions of trans-β -methylstyrene reached
presence of molecular oxygen as an oxidant. In addition, various
97% with selectivity of 100%.
parameters such as catalyst amount, different catalyst types, re-
Instability and coagulation of unsupported CuO NPs are impor-
action temperature, reaction time, reusability and stability of the
tant issues that limit their catalytic application in oxidation reac-
catalyst were investigated. High conversion and selectivity were
tions. Consequently, much attention has been focused on the syn-
obtained at 393 K at reaction time of 6 h.
thesis of supported CuONPs. For example, synthetic Ag nanowires
Nanostructured cobalt oxide can be inserted in the pores of
were used as a support in order to carry CuO NPs [186]. CuO@Ag
mesoporous silica (MCM-41) via ultrasound radiation method. In
nanowires exhibited excellent catalytic performance when used as
one special research, CoO–MCM-41 nano-catalyst was prepared a catalyst in both epoxidation of trans-stilbene and oxidation of
ultrasonically from cobalt carbonyl, [Co(CO)3 NO], as the precur- various alcohols in the presence of air and tert-butyl hydroper-
sor [173]. This catalyst was utilized in epoxidation of olefins ac- oxide (TBHP) as the oxidant, respectively. The effectiveness of
cording to Mukaiyama’s method [174] in the presence of isobu- CuO@Ag nanowires as a catalyst in epoxidation of trans-stilbene
tyraldehyde as the reductant. was tested in different organic solvents such as DMF, Dioxane,
O-Xylene, toluene and isopropylbenzene. O-Xylene was chosen
2.7. Group 11 elements (Cu, Ag and Au) as the best solvent with 99% conversion and good selectivity in
this reaction. When O-Xylene was utilized as the solvent, GC–MS
2.7.1. Copper oxide nanoparticles analysis showed 2-methylbenzaldehyde, o-tolylmethanol, and 2-
CuO can be recognized as one of the most important transition methylbenzoic acid as byproducts which enabled Cao and cowork-
metal oxides in a broad range of material science [175]. Different ers to propose a logical reaction mechanism. The reaction mecha-
synthetic methods lead to the formation of CuO NPs with various nism is depicted in Fig. 29. As seen in Fig. 29, O-Xylene has a crucial
shapes and morphologies such as nanotubes [176], nanorods [177], role in the formation of unstable free radical intermediates with
hollow microspheres [178], nanospheres [179], aligned nanowires active oxygen on the surface of CuO@Ag nanowires. Subsequently,
[180], nanocages [181], microflowers [182] and dandelions [183]. peroxide is formed and used as an oxidant in the epoxidation of
In one report [184], urchin-like CuO NPs with self-assembled trans-stilbene.
nanostrips were synthesized using a facile reflux method. In this In addition, the versatility of CuO@Ag nanowires as the catalyst
method, Cu(NO3 )2 ·3H2 O and urea as starting materials were dis- was investigated in the oxidation of alcohols to the corresponding
solved in the mixture of distilled water and ethylene glycol mono- aldehydes, carboxylic acids or ketones in the presence of TBHP and
methyl ether followed by heating the mixture at 100 ◦ C for 6 acetonitrile as oxidant and solvent, respectively.
h. Different copper salt sources and the preparation method af- Sumitomo process [187] has been known as practical method
fected shape and morphology of the synthesized CuO particles. for the preparation of propylene oxide from propene. In this
On the other hand, unlike copper nitrate, the use copper sulfate method, cumene (CUM) is used to produce cumyl hydroper-
and copper chloride as precursors led to CuO NPs with rod-like oxide (CHP) to promote the epoxidation reaction. Ravasio and
and octahedral shapes, respectively. In the case of preparation coworkers utilized this method in the presence of CuO/Al2 O3 bi-
method, it must be mentioned that conventional methods lead to functional nanomaterials as the catalyst [188]. Highly dispersed
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 O2 [190]. The sol–gel method was used for preparation of Cs+ -
by chemisorption–hydrolysis method. Then the catalytic activity modified CuOx /SiO2 catalyst. In this process, an aqueous solution
of these NPs was studied in one-pot epoxidation of some olefins. of Cs+ ion was mixed with the aqueous solution of Cu(NO3 )2 in
Reaction scheme for epoxidation of trans-stilbene is shown in the presence of ethylene glycol followed by dropwise addition of
Fig. 30. tetraethyl orthosilicate. The final product as catalyst was obtained
For comparison, bare Al2 O3 and CuO/SiO2 were also used as after calcination for 6 h at 823 K. For comparison, the catalytic
catalysts in the epoxidation reactions. Results showed that these performance of different alkali-metal-ion-modified CuOx /SiO2 was
materials are poorly active or fully inactive, suggesting that Al2 O3 also investigated. Results demonstrated that only the selectivity to
and CuO have a synergistic effect in the oxidation reaction. Ad- PO increased by changing the alkali ion from Li+ to Cs+ and there
ditionally, the stability and reusability experiments showed that was no obvious trend in the change of propylene conversion. In the
the CuO/Al2 O3 catalyst can be used for more than 3 times in the aforementioned study, the Cs/Cu molar ratio and reaction temper-
conversion of stilbene to the corresponding epoxide with only a 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
slight loss of catalytic activity.
on kinetic studies, the reaction pathways shown in Fig. 31A and
Epoxidation of styrene to styrene oxide was also studied by
31B are proposed for the oxidation of propylene by CuOx /SiO2 and
supported copper oxide in the presence of TBHP. In one report, the
Cs+ -modified CuOx /SiO2 , respectively. The oxidation of propylene,
catalytic effect of different CuO supports such as CuO/Si-MCM-41,
as a substrate occurred in both vinyl and allyl positions to give
CuO/Al2 O3 , CuO/Ga2 O3 and CuO/In2 O3 was investigated [189]. Fur-
PO and acrolein as the primary products. Based on Fig. 29A, these
ther, anhydrous or aqueous TBHP significantly affected selectivity primary products were obtained with CuOx /SiO2 as the catalyst in
and yield of the products. Other studies showed that the CuO/In2 O3 the presence of O2 . The isomerization of PO to allyl alcohol followed
catalyst had better performance in epoxidation by anhydrous TBHP by oxidation to acrolein is recognized as the drawbacks of working
but the catalytic activity of CuO/Ga2 O3 was better in epoxidation with CuOx /SiO2 as the catalyst which significantly decreased the
by aqueous TBHP. Otherwise, CuO/SiO2 had better performance in PO yield. In the case of Cs+ -modified CuOx /SiO2 , the existence of
epoxidation by both anhydrous and aqueous TBHP. Cs+ not only prevented the consecutive conversion of PO but also
The low catalytic activity of SiO2 supported copper oxide, increased the selectivity to PO and yield of acrolein, as depicted in
CuO/SiO2 , was reported in the epoxidation reaction [188]. Using Fig. 31.
alkali metal ions as a promoter can be considered a novel strat- The same authors reported other copper oxide based catalytic
egy to improve the catalytic activity of CuOx /SiO2 . For instance, systems such as CuOx /SBA15 and CuOx -SiO2 modified by K+ which
Wang and colleagues utilized Cs+ as the most efficient promoter were used in the oxidation of propylene to propylene oxide
of CuOx /SiO2 for epoxidation of propylene to propylene oxide by [191–193].
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].
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 carbons of the neighboring adsorbed styrene molecules. Oxamet-
oxides were synthesized and utilized for the oxidation of benzyl allacycle underwent two different pathways simultaneously. One
alcohol in the presence of H2 O2 as an oxidant [194]. pathway was the rearrangement to form styrene oxide and the sec-
As seen from Fig. 32, CuO/SBA-15-C1 was prepared directly by ond pathway was the reaction with radicals to get benzaldehyde.
the reaction of Cu (II) ions with surface silanol groups onto silica The second pathway can be eliminated by the addition of Na2 CO3
followed by calcination at 500 ◦ C. But in the case of CuO/SBA-15-C2 as a hydroxyl radical scavenger which increased the conversion of
SBA-15 was treated first by 3-[bis[(2-hydroxyethyl)amino] propyl- styrene and selectivity for styrene oxide.
triethoxysilane] (PADOH) and Hexamethyldisilazane (HMDS) to For the first time, Pande and coworkers developed a new
produce Cu(II)-PADO-HMDS-SBA-15. Then, the as-prepared mate- method to synthesize nanocomposites of CuO and Cu(0) supported
rial was calcined at 500 ◦ C. It must be highlighted that the forma- on cation exchange resin-bound NPs [197]. In this approach, CuSO4
tion of oligomeric copper spices which produce metallic aggregates aqueous solution was employed as the Cu2+ ions precursor which
did not occur when the surface of SBA-15 was modified with exchanged H+ with the cationic resin. Depending on the type of re-
PADOH and HMDS. The catalytic performance of these materials ducing agent, Cu(0) or CuO could be produced on the resin matrix.
for the title reaction showed 83% and 82% selectivity toward ben- Conversely, Cu(0) was produced by using aqueous borohydride or
zaldehyde over CuO/SBA-15-C1 and CuO/SBA-15-C2, respectively. hydrazine and surprisingly CuO was obtained with an alkaline so-
Recently, new bimetallic oxide systems based on copper oxide lution of cyclodextrin (CD). In this case, CD not only facilitated the
are the subject of ongoing research. In one report, an efficient NiO formation of CuO by decreasing the activation energy, but also con-
promoted CuO–NiO/SBA-15 catalytic system was developed using trolled the growth of CuO NPs with its capping property [198]. The
the ultrasonic post-grafting method [195]. SBA-15, with amine catalytic activity of as-prepared catalysts was investigated for the
oxidation of various alcohols in air. Experimental results demon-
groups on its internal surfaces, can absorb the starting materials
strated that the CuO nanocomposite has a remarkable efficiency
into its mesoporous channels under ultrasonic conditions. In this
compared to the corresponding Cu(0) and commercial CuO. The
system, NiO not only improved the distribution of CuO–NiO in the
aggregation tendency of nanoparticle catalysts is a major obstacle
mesoporous channels of SBA-15, but also increased the catalytic
for their practical use under catalytic reactions. In one report, well-
activity of copper oxide. The catalytic activity of CuO–NiO/SBA-15
dispersed CuO colloidal nanocrystal clusters (CNCs) were prepared
was compared with other catalysts such as CuO/SBA-15, NiO/SBA-
by a simple one-pot solvothermal method and used for olefin
15 and SBA-15 in the epoxidation of styrene as a model reaction
epoxidation in the presence of TBHP as an oxidant [199]. In order
in the presence of TBHP. In the case of monometallic species like
to prevent the aggregation of CuO CNCs as well as to improve their
CuO/SBA-15 and NiO/SBA-15, the conversion, selectivity and the stability, mesoporous SiO2 was utilized as a protective coating shell
yield of this reaction was low. Interestingly, the conversion and to form CuO CNCs@meso-SiO2 nanocomposites. Fig. 34 depicts the
selectivity of styrene to styrene oxide improved to 73.6% and 83.2%, synthetic scheme of CuO CNCs@meso-SiO2 nanocomposites.
respectively, with the incorporation of NiO. These preliminary The catalytic performance of CuO CNCs@meso-SiO2 nanocom-
results demonstrated an obvious synergistic effect in NiO–CuO posites were compared with CuO CNCs and Cu2 O hollow
system. Moreover, the molar ratio of Ni/Cu affected the conversion, nanospheres for norbornene epoxidation using TBHP and ace-
selectivity and yield of this reaction. CuO–NiO/SBA-15 with 0.34 tonitrile as the oxidant and solvent, respectively. All catalysts
molar ratio of Ni/Cu had the best catalytic performance with 100% had 100% selectivity for norbornene epoxidation to the corre-
conversion and 92.3% selectivity. Other olefins such as norbornene, sponding product. But the conversion was 90, 86 and 82.3% using
trans-β -methylstyrene, trans-stilbene and cis-cyclooctene were CuO CNCs@meso-SiO2 nanocomposites, CuO CNCs and Cu2 O hol-
also oxidized in the presence of CuO–NiO/SBA-15 catalyst. Olefins low nanospheres, respectively. Additionally, epoxidation of other
bearing electron-donating substitutes can absorb onto the vacant olefins were also tested in the presence of these catalysts. The
coordination sites of metal oxides and increase the activity of CuO CNCs@meso-SiO2 nanocomposites showed excellent catalytic
the double bonds of the olefins [196]. The order of reactivity performance even after eight runs.
was trans-stilbene > trans-β -methylstyrene > norbornene > cis- Recently, Wang and colleagues developed a new copper oxide
cyclooctene. In the proposed mechanism, the olefin substrate and based hybrid nano-catalyst which consisted of iron oxide mag-
TBHP were absorbed into the channels and on the metal oxide netic NPs (Fe3 O4 ) and mesoporous silica (meso-SiO2 ) as the core
surface, respectively. Next as shown in Fig. 33, oxametallacycle and protective shell, respectively [200]. The synthetic process for
was formed via insertion of peroxidic groups between secondary Fe3 O4 –CuO@meso-SiO2 microspheres is illustrated in Fig. 35.
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 mixture by an external magnet but also promoted catalytic activity
Fe3 O4 NPs with polyacrylic acid (PAA). The existence of carboxylic of the catalyst with its electron-donating properties [201]. The
acid groups on the surface of Fe3 O4 facilitated the deposition of SiO2 layer with its mesoporous structure inhibited aggregation
copper ions in the presence of PVP and urea. Finally, a template- of NPs via a physical protective shell. Moreover, the small size
assisted sol–gel technique was used to deposit a silica protective of the pores of the silica shell compared with CuO and Fe3 O4
shell. Fe3 O4 –CuO@meso-SiO2 microspheres showed excellent per- prevented CuO and Fe3 O4 from leaching. It is worth highlighting
formance in the epoxidation of olefins in the presence of TBHP as that mesoporous SiO2 with ordered channels acts as nano-reactors
a green oxidant in acetonitrile. Fe3 O4 and SiO2 played critical roles by adsorbing reagents and accelerating the mass transfer. To inves-
in catalytic activity of Fe3 O4 –CuO@meso-SiO2 . On the other hand, tigate the general applicability of the Fe3 O4 –CuO@meso-SiO2 cata-
Fe3 O4 not only facilitated separation of catalyst from the reaction lyst, some other olefin derivatives were also studied. Experimental
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)

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
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]
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]
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]
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]
CuO–NiO/SBA-15 Olefins Oxidant: tert-butyl Epoxides [196]
CuO CNCs@meso-SiO2 nanocomposites Olefins Oxidant: tert-butyl Epoxides [199]
Fe3 O4 –CuO@meso-SiO2 microspheres Olefins Oxidant: tert-butyl Epoxides [200]
CuO nanorods Olefins Oxidant: tert-butyl Epoxides [202]
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- 2.8. Other metal oxides
ide products. These unique properties of Fe3 O4 –CuO@meso-SiO2
catalyst originates from synergistic effects of Fe3 O4 , CuO and 2.8.1. Cerium oxide nanoparticles
SiO2 . Cerium dioxide NPs (CeO2 NPs) with an average size of 15 nm
As mentioned previously, the morphology and shape of NPs was synthesized and employed as an environmentally friendly
as a catalyst play a crucial role in their catalytic activity. For ex- heterogeneous catalyst for the aerobic oxidation of para-xylene
ample, CuO nanorods were obtained using a simple hydrothermal to terephthalic acid in water by Deori and coworkers [203]. The
protocol [202] and the as-prepared CuO nanorods were used as a catalytic activity of as-prepared CeO2 NPs was compared with the
catalyst in the oxidation of cyclohexene in the presence of TBHP commercially available bulk CeO2 materials. The highest activity
in acetonitrile. Surprisingly, as shown in Fig. 36, a nearly 100% of CeO2 NPs could be related to their small crystallite size (15 nm)
cyclohexene conversion with 95% selectivity of 2-cyclohexene-1- which provided a very high surface area as well as a large number
one was achieved. Conversely, less than 5% selectivity of the epoxy of pores. Additionally, Cetyl tri-methyl ammonium bromide (CTAB,
product was achieved. 99%) was used as an ionic surfactant in the preparation of CeO2 NPs
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Transition Metal Oxide Nanoparticles As Efficient Catalysts in Oxidation

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

Contents lists available at ScienceDirect

Nano-Structures & Nano-Objects

Transition metal oxide nanoparticles as efficient catalysts in oxidation

highlights graphical abstract

• A comprehensive review of transi-

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

Fig. 6. Disproportionate decomposition of the side-on peroxide under UV irradia-

results demonstrated that TiO2 and SiO2 /TiO2 photocatalysts pre-

(B) WO3 /TiO2 .

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

solvents (acetonitrile and toluene) and temperatures 353 and 383

Fig. 15. Possible epoxidation reaction mechanism [110].

Fig. 16. Possible main-product and by-products of epoxidation of cycloocta-1,5-diene [115].

oxidative dehydrogenation of the aldimines to nitriles (step 3),

Two different types of manganese oxide NPs, Mn2 O3 and

Fig. 23. Preparation method for hematite nanoparticles [149].

was the use of PEG as a surfactant which had a direct influence on

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

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

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

(continued on next page)

[1] A.M. Thayer, Chem. Eng. News 70 (1992) 27.

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