See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/284727255

Catalysis: A brief review on Nano-Catalyst

Article · August 2014

CITATIONS READS

37 31,326

2 authors:

Santosh BAHADUR Singh Praveen K. Tandon

National Institute of Technology Raipur University of Allahabad
45 PUBLICATIONS   287 CITATIONS    65 PUBLICATIONS   529 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

this is my research paper View project

Catalyzed synthesis and purification of water with nanoparticles View project

All content following this page was uploaded by Santosh BAHADUR Singh on 27 November 2015.

The user has requested enhancement of the downloaded file.

Journal of Energy and Chemical Engineering Aug. 2014, Vol. 2 Iss. 3, PP. 106-115

Catalysis: A Brief Review on Nano-Catalyst

Santosh Bahadur Singh*1, Praveen Kumar Tandon2
Department of Chemistry, University of Allahabad, Allahabad-211002, U.P., India
*1
[email protected]; [email protected]

Abstract-Catalysis is one of the most valuable principles out of twelve principles of Green Chemistry. Green chemistry is the
utilization of a set of principles that eliminates or reduces the use or generation of hazardous substances in the design, manufacture,
and application of chemical products and emphasizes hazard reduction as the performance criteria while designing new chemical
processes. In recent years, nanocatalysis has become an emerging field of science due to its high activity, selectivity and productivity.
The nanoscale size, shape and an exceptionally large surface area to volume ratio imparts unique properties to nanocatalysts because
of the structural and electronic changes which differentiates them from the bulk materials. This mini-review mainly focused on
describing the fundamental understanding of nanocatalysis, how unique catalytic property and other specific properties of
nanomaterials depend on its size and structure at the atomic level.
Keywords- Catalysis; Nanocatalysis; Green Chemistry; Homogeneous; Heterogeneous

I. INTRODUCTION
Catalysis plays a central role in chemical transformations and lies at the heart of countless chemical protocols, from
academic research at laboratories level to the chemical industry level [1]. By using catalytic reagents, one can reduce the
temperature of a transformation, reduce reagent-based waste and enhance the selectivity of a reaction that potentially avoids
the unwanted side reactions leading to a green technology. In 1998, Anastas and Warner [2] suggested a set of twelve
principles which is the main philosophy of Green chemistry to reduce or eliminate chemicals and chemical processes that have
negative environmental impacts. Designing and developing ideal catalysts is one of the very important concepts of green
chemistry. According to these principles catalytic reagents (as selective as possible) are superior to stoichiometric reagents.
Stoichiometric reagents are used in excess and work only once while catalytic reagents used in small amounts and can carry
out a single reaction many times. To work more like nature is the base of all the twelve principles of green chemistry. Nature
clearly provided hints to us to carry out environmentally benign reactions by using micro-organisms and/or enzymes.
In the absence of catalyst, variety of products i.e. medicines, fine chemicals, polymers, fibres, fuels, paints, lubricants, and
a myriad of other value added products essential to humans, would not be feasible. Catalysis contributes the mechanism by
which chemical transformations take place thus enabling the commercially viable creation of desired materials. Thus, by using
catalysts manufacturing protocols can be made more economic, green and sustainable [3]. Apart from heavy metal catalysts
which are mostly not recoverable from system, softer catalysts like zeolites, phase transfer catalysts, e.g., crown ethers, are
found more industrial applications.
Among three well-known catalysis categories e.g. homogeneous, heterogeneous and enzymatic catalysis, enzymatic
catalysis is the most efficient and greenest catalysis found in nature. Both the homogeneous and heterogeneous catalysis has its
own merits and demerits due to which there is urgent need of a new catalytic system, which should be active like homogeneous
catalysis, and should also be easily recoverable like heterogeneous catalyst [4]. Nano-catalysts have combined advantages of
both the homogeneous and heterogeneous catalytic systems. Nano catalytic system allows the rapid, selective chemical
transformations with excellent product yield coupled with the ease of catalyst separation and recovery. Recovery of catalysts
from the system is most important characteristics of any catalyst before being acceptable for green chemical manufacturing
processes in industry. Because of nano size (high surface area) the contact between reactants and catalyst increases
dramatically (this phenomenon is close to homogeneous catalysis). Insolubility in the reaction solvent makes the catalyst
heterogeneous and hence can be separated out easily from the reaction mixture (this phenomenon is close to heterogeneous
catalysis) [5-9].

II. CHEMISTRY OF NANOPARTICLES

Nanoparticles (NPs) are particles sized between 1-100 nano-meters (10-9 meters). Synthesis of stabilized nanoparticles
sized between 1-100 nm is the main task of the nanochemistry. Nanoparticles may be synthesized by various means categories
in two major heads like (i) top-down technologies and (ii) bottom-up technologies [10, 11] (Scheme 1). Various sophisticated
instruments have been used to characterize the nanomaterials to find out actual size, shape, surface structure, valency, chemical
composition, electron band gap, bonding environment, light emission, absorption, scattering and diffraction properties which
includes nuclear magnetic resonance spectroscopy (NMR), infra red spectroscopy (IR), ultra-violet and visible spectroscopy
(UV-Vis), transmission electron microscopy (TEM), scanning tunnelling microscopy (STM), scanning electron microscopy
(SEM), energy dispersive X-ray spectrometer (EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS),
ultraviolet photoelectron spectroscopy (UPS), extended X-ray adsorption fine structure spectroscopy (EXAFS), X-ray
absorption near-edge spectroscopy (XANES), X-ray emission spectroscopy (XES), photoluminescence spectroscopy (PL),

- 106 -
Journal of Energy and Chemical Engineering Aug. 2014, Vol. 2 Iss. 3, PP. 106-115

small angle X-ray scattering (SAXS), atomic force microscopy (AFM), , etc [12].

Synthesis of Nanoparticles

Top-down technologies Bottom -up technologies

Mechanical grinding Sol-gel

Chemical reduction of salts
Metal vapour Precipitation
Solvothermal processing
Thermal breackdown
Electrochemistry
Chemical breackdown Template directed
Sonochemistry
Spontaneous chemisorption Microwave irradiation
Microemulsion

Scheme 1: Various ways to synthesize nanoparticles

As restriction arises in its definition about its size, the chemistry of nanoparticles mainly depends on two things i.e. (i)
synthesis of NPs well controlled in size and shape and (ii) molecular approach to find more selective applications of NPs
especially in nanocatalysis.
Synthesis of NPs in well controlled size is mainly made by using different stabilizing agents or capping agents i.e. ligands
(thiols, phosphines, amines), surfactants (ammonium salts), polymers (polyvinyl alcohols, polyvinyl pyrrolidone, block-
copolymers), dendrimers (polyamidoamine), ions, polyoxoanions, etc [13-15]. Appropriate choice of the protecting/stabilizing
agents is also a very important factor because these can alter the surface properties of the NPs, as it can modify the nature of
active sites (morphology) and the surface chemical environment (steric and/or electronic effect) [16-19]. Selectivity and
reactivity of the NPs has a critical importance as it can influence the course of a reaction which mainly depends on surface
state of NPs. Thus, selectivity and reactivity of NPs depends on mainly two concerns e.g. (i) control of crystal structure and
morphology and (ii) control of surface composition [20-22]. Activity of NPs is concern of (i) surface structure, (ii) exposure of
different crystallographic facets and increased no. of edges, corners & faces [23, 24]. Therefore, efficient control of
morphology of the nanoparticles is becoming an interesting task all over the world in recent years
Second, the selectivity of NPs can also be altered by controlling its intrinsic composition. For example, synthesis of alloyed
versus core-shell bimetallic NPs or the synthesis of NPs with a well-defined surface state are key points of current days
nanoscience research and development. Bimetallics are very emerging and new field of nanocatalysis [25, 26]. They are not
only expecting to show combined properties of two distinct metals but also new properties and capabilities due to a synergy
between the two metals. The properties of nanocrystals are also dependent on the surface chemistry. Chemical modifications of
nanoparticles, such as by the use of ligands or diatoms to decorate their surface can thus provide new catalytic properties [21].
Thus, one can expect to be able to modify the chemical properties of nanoparticles by an appropriate choice of the capping
agents, due to their own electronic or/and steric properties. For example, in asymmetric catalysis, the chiral capping agent used
for the stabilization of metallic nanoparticles is of fundamental importance as it is expected to induce enantioselectivity.
With parallel to progress in the efficiency of metallic nanoparticles, progress has also been made in their recovery and
recyclability [27]. Recyclability of catalyst behaves like the bottleneck for industrial application of NPs in the solution phase.
For this purpose, the deposition of pre-formed NPs onto supports (silica, alumina, titania, clay, biowaste materials, ceria or
other oxides as well as carbon supports in various forms i.e. mesostructured silica [28], alumina membranes [29], carbon
nanotubes [30] to get heterogeneous systems easy to recover is being explored. But a new trend appeared in the past few years
which consists of the use of magnetic supports to recover the catalyst from the catalytic media by simply applying a magnet.
Indeed, magnetic separation has emerged as a robust, highly efficient and fast separation tool with many advantages compared
with product/catalyst isolation by means of other chemical or physical procedures, such as liquid–liquid extraction,
chromatography, distillation, filtration or centrifugation [31]. The catalyst immobilized on super paramagnetic nanomaterials
can be easily separated from the products due to a strong interaction between the magnetic nanoparticles and an external
applied magnetic field, and it can be easily re-dispersed in the absence of the magnetic field due to the absence of magnetic

- 107 -
Journal of Energy and Chemical Engineering Aug. 2014, Vol. 2 Iss. 3, PP. 106-115

memory.

III. NANO-CATALYSIS
Catalysis is one of the pioneer applications of nanoparticles. Various elements and materials like aluminium, iron, titanium
dioxide, clays, and silica all have been used as catalysts in nanoscale for many years. But appropriate explanation of its
tremendous catalytic behaviour showing by NPs still has not been fully understood. Large surface area of nanoparticles has a
straight forward positive effect on reaction rate and may also be a reasonable explanation of its catalytic activity. Structure and
shape-based properties of any materials at its nanoscale size can also effect the catalytic activity of a material. The fine tuning
of nanocatalysts, in terms of composition (bimetallic, core-shell type or use of supports), shape and size has accomplished
greater selectivity. Thus the question here is how the physical properties of nanoparticles affect their catalytic properties, and
how fabrication parameters can in turn affect those physical properties. By better understanding of these, a scientist can design
nanocatalysts which are highly active, highly selective, and highly resilient. All these advantages will enable industrial
chemical reactions to become more resource efficient, consume less energy, and produce less waste which help to counter the
environmental impact caused by our reliance on chemical process [32-36]. Nanoparticles are recognized as the most important
industrial catalyst and have wider application ranging from chemical manufacturing to energy conversion and storage. Variable
and particle-specific catalytic activity of nanoparticles is due to its heterogeneity and their individual differences in size and
shape. Scheme 2 represents basic difference in bulk catalysis and catalysis shown by nanoscale materials.
Catalytic activity of materials-How it is depend on the size of materials?
Catalysis

1-10 nm
Nanomaterials
Homogeneous Nano-Catalysis Heterogeneous
Catalysis Catalysis
Merits: Merits:
High activity
1. High activity 1. Excellent stability
High selectivity
2. High chemo-and regio- 2. Easy accessibility
selectivity Excellent stability
3. Easily seperable
Demerits: Easily separable
Demerits:
Cumbersom product purification Energy efficient
and difficulty in catalyst recovery Inferior catalytic activity
Atom economy relative to their counterpart
homogeneous and requires
more reaction time.

Scheme 2: Comperative efficiency of homogeneous, heterogeneous and nanocatalysis

IV. CONCEPT OF NANOCATALYSIS

Concept behind the nanocatalysis may be understood by considering the impact of the intrinsic properties of nanomaterials
on catalysis (Scheme 3) [37-41]. Intrinsic properties of nanomaterials that have a vital impact on their catalytic activity may be
categorized as (i) quantities that are directly related to bond length, such as the mean lattice constant, atomic density, and
binding energy. Lattice contraction in a nano-solid induces densification and surface relaxation., (ii) quantities that depend on
the cohesive energy per discrete atom, such as self-organization growth; thermal stability; coulomb blockade; critical
temperature for phase transitions, and evaporation in a nano-solid; and the activation energy for atomic dislocation, diffusion,
and chemical reactions, (iii) properties that vary with the binding energy density in the relaxed continuum region such as the
Hamiltonian that determine the entire band structure and related properties such as band gap, core level energy, photo-
absorption, and photoemission and (iv) properties from the joint effect of the binding energy density and atomic cohesive
energy such as the mechanical strength Young’s modulus, surface energy, surface stress, extensibility and compressibility of a
nano-solid, as well as the magnetic performance of a ferromagnetic nano-solid [42].

- 108 -
Journal of Energy and Chemical Engineering Aug. 2014, Vol. 2 Iss. 3, PP. 106-115

Structural parameters
Cohesive energy per discrete atom
Binding energy density

Composition and Band Gap

Oxidation State
Effect Band Structure Lattice Parameters

Mechanical Atomic Density

Properties Shape, Size and
Binding Energy
Interparticle
Magnetic Intrinsic properties Distance Effect
Properties of nanomateials

Activation Energy

Phase Transition

Support and Confinement

Effect

Scheme 3: Effect of intrinsic properties of nanomaterials on its

catalytic activity

Performance of solid materials or a cluster of atoms vary from that of an isolated atom mainly due to the involvement of
inter-atomic interactions. Adjustment of the relative number of the under-coordinated surface atoms provides an additional
freedom that allows one to tune the properties of a nano-solid with respect to that of its bulk counterpart. Hence, contribution
from the under-coordinated atoms and the involvement of inter-atomic interaction can be the starting point of consideration to
bridge the gap between an isolated atom and a bulk solid in chemical and physical performances. The impact of atomic
coordination reduction (deviation of bond order, length, and angle) is tremendous. It unifies the performance of a surface, a
nano-solid, and a solid in amorphous state consistently in terms of bond relaxation and its consequences on bond energy. The
unusual behaviour of a surface and a nano-solid has been consistently understood and systematically formulated as functions of
atomic coordination reduction and its derivatives (size dependence) on the atomic trapping potential, crystal binding intensity,
and electron–phonon coupling [43, 44].
By precisely controlling the size, shape, spatial distribution, surface composition and electronic structure, and thermal and
chemical stability of the individual nano components, it can be widely used in catalysis with newer properties and activity.
Nanostructured catalysts have been the subject of considerable academic and industrial research attention in recent times due to
the numerous potential benefits that can accrue through their use (Scheme 4).

Energy Efficient Minimum Chemical Waste

Super Catalysts Nano

& catalysis Reduce Global Warming
Reagents

Improved Economy Water Remediation

Scheme 4: Benefit's of nanocatalysis

- 109 -
Journal of Energy and Chemical Engineering Aug. 2014, Vol. 2 Iss. 3, PP. 106-115

V. HOMOGENEOUS AND HETEROGENEOUS NANOCATALYSIS

Nano-catalyst in homogeneous system typically means a solution or suspension of nanoparticles in a solvent. But in
homogeneous nanocatalysis (catalyst which is in a same phase to the reactants), it is a must to consider how to prevent its
aggregation when designing a nano-catalyst for use in a solution. Nanoparticles have a special characteristic to aggregate and
will clump together to form larger particles, if it is not prevented properly, nanoparticles lose their large surface area and other
benefits. Polymer-based stabilization of nano-particles to prevent its aggregation is recognized as most effective way to
stabilize nanoparticles in solution. Long chain molecules make it impossible for the nanoparticles to come in contact to
aggregate or clump together to form larger particles. However, such stabilization decreases the overall catalytic activity of
nano-catalyst by reducing the availability of the nano-particle surface for the reacting molecules [45].
Recovery of nano-catalyst from the system is another major concern of homogeneous nanocatalysts. It is notoriously
difficult to remove nanoparticles from a solution, and the extra steps needed to do so could completely negate the process
simplification due to using the catalyst in the first place. Non-recoverability of homogeneous nanocatalysts poses an
environmental risk (most nanoparticles cannot be destroyed by incineration and the effects of nano-particle accumulation in
ecosystems are largely unknown) as well as threatening the profitability of the process [46, 47, 3].
Heterogeneous catalysis (catalyst which is in a different phase to the reactants) is always considered as more
environmentally friendly catalysis due to its high recoverability. The heterogeneous catalyst may be usually a solid or
immobilized on a solid inert matrix. Research to investigate the catalytic potential of various nano-particle-support systems has
attracted more attention of scientific community nowadays. Recent examples include copper, ruthenium; rhodium, silver,
palladium, iron, gold, nickel and platinum nanoparticles and supports used range from silica, clays, zeolite and alumina or
biowaste materials to carbon fibres. Nanostructured solids are another explored area of heterogeneous nanocatalysts.
Nanoporous materials can be manufactured by growing the solid material around a molecular template. Nanoscale features can
also be etched into the surface of a catalyst using standard lithography techniques - this can allow a degree of control over
reactant flow on the catalyst surface, as well as increasing surface area [48].
One of the most interesting scientific and technological challenges associated with the use of nanoparticles as catalysts is
the understanding of how the composition and atomic-scale structure of nanoparticles produce the best catalytic activity. The
second challenge is to synthesize these particles with maximum control over the composition and structure. Modern
nanotechnology methods clearly offer a great potential for future developments in both characterization and synthesis of
heterogeneous catalysts based on supported nanoparticles [49].
Bi and Lu [50] reported the catalytic activity of nanoscale copper in production of hydrogen from formaldehyde at room
temperature and also suggested a possible reaction pathway for this conversion (Scheme 5).

H H OH Cu-Nps H
C O + H-OH C C O + H2
H H OH NaOH OH
Formaldehyde Formic acid
Intermediate

Scheme 5: Nanoscale copper catalyzed production of hydrogen

Nagpal et al. [51] reported the reductive dechlorination of lindane (-hexachlorocyclohexane) in aqueous medium catalysed
by nanoscale Fe-Pd bimetallic particles (Scheme 6). Presence of palladium on the surface of nanoscale iron particles increased
the catalytic activity of Fe-Pd bimetallic system to enhance the dechlorination of lindane. Dechlorination occurs via adsorption
of chlorinated compounds (lindane) on the particle surface [52]. Palladium on the surface acts as a collector of hydrogen gas
that is produced by reduction of water molecule in presence of nanoscale iron (iron corrosion reaction). Nanoscale palladium
(Pd0) reacts with hydrogen gas to form either metal hydride or hydrogen radicals. Both are highly reactive towards C–Cl bonds
and finally replace the entire chlorine atoms from lindane to form cyclohexane.

Pd0
2H + C6H6Cl6
2+ -
Fe0 + 2H2O Fe + 2OH + H2 C6H12
2Pd-H + C6H6Cl6 Cyclohexane
Pd0 Lindane
Scheme 6: Nanoscale Fe0-Pd0 bimetallic nanoparticle catalyzed dechlorination of lindane
Gawande et al. [4] reported the use of surface functionalized nano-magnetite supported nanoparticles in catalysis, green

- 110 -
Journal of Energy and Chemical Engineering Aug. 2014, Vol. 2 Iss. 3, PP. 106-115

chemistry and pharmaceutically significant reactions. These nanoparticles act as bridge between heterogeneous and
homogeneous catalysis. Magnetite-supported metal nanocatalysts have been successfully used in organic synthesis for a variety
of important reactions [53-56] (Scheme 7).

Few selective nano-catalysed reactions are summarized in Scheme 8 [57-68] which highlights the application of nano-
catalysts in organic synthesis.
Nanocatalysts

[57]
[58]
Deoxygenation of epoxides Gold Synthesis of 1,2,3-triazole

[59] [60]
Photodegradation of Synthesis of highly
2,4,6-trinitrophenol Calcium oxide substituted pyridines

[61] [62]
C-C coupling reactions Hiyama coupling reactions
Palladium of benzyl halides

Synthesis of some aromatic [63]

[64] Synthesis of phenols,
aldehydes and acids Copper anilines, thiophenols
from aryl halides

[65] [66] One-pot synthesis of

Synthesis of pyranopyrazoles Zinc oxide caumarins through
Knoevenagel condensation

[67] [68]
Diels Alder cycloadditions
One-pot synthesis of Silver of 2-hydroxychalcones
benzofurans

Scheme 8: Few selective nanocatalyzed organic reactions using various nanoparticles

- 111 -
Journal of Energy and Chemical Engineering Aug. 2014, Vol. 2 Iss. 3, PP. 106-115

VI. FUTURE ASPECTS OF NANOCATALYSIS

As it’s known, catalysis is also a very old field of chemical research but still now it is very active research field due its own
merits. Development of the nanoscience opens new opportunities in this area. Application of nanoparticles as a catalyst is not
very new, but our ability to image and characterize it in respect to its catalytic activity has been increased nowadays. Concept
of nanocatalysis is known since the 1950s when the term nanotechnology was not even known [69, 70]. In 1986, first time
Haruta et al. [71] reported the catalytic activity of gold (Au) nanoparticles in oxidation of carbon monoxide and hydrogen at
low temperatures. After this reporting, a very old conventional idea about gold for its inertness towards chemical reaction has
been completely changed and a new door to interesting applications of nanoscale materials in catalysis is opened.
Nanocatalysis has the advantage of both homogenous and heterogeneous catalysis i.e. high catalytic activity (turn over
frequency TOF) and selectivity like homogeneous catalysis, re-cyclization and separation of catalyst after completion of
reaction making it closer to the heterogeneous catalysis. Traditional heterogeneous catalyst systems have two main drawbacks
compared to their homogeneous counterparts is (i) the reduced surface area that is accessible to reactant molecules, thereby
limiting their catalytic activities [72] and (ii) leading to an unnecessarily high consumption of expensive catalyst materials [73].
Nano-scaled catalytic materials can solve these problems by increasing the surface to volume ratio (S/V) [74, 75]. These
specifications are the base of present status of nanocatalysis.
Advances in nanocatalysis in past few years with present day’s developments open a new vision for nanocatalysis and its
future aspects such as inspired design, synthesis and formulation of industrially and biologically important catalytic materials.
Apart from these future aspects of nanocatalysis, its energy and environmental concerns will also receive attention.

VII. CONCLUSIONS
Nanocatalysis plays a central role in both the academic as well as industrial research and development. Industrial impact of
nanocatalysis is clearly reflected by the increasing number of nanocatalysis related patents, technologies and products in the
market. Size and shape controlled preparation of metal nanoparticles are very promising for greener heterogeneous catalytic
reactions. On the basis of better understanding of size and shape effects of the nanoparticles and their interactions with support
materials or stabilizing agent, today it is very promising that scientists are able to solve current environmental, social and
industrial problems. Thus, I hope this review provide a brief information about nanocatalysis and also inspire research and
development in this field.

ACKNOWLEDGMENT

The author (S.B. Singh) is grateful to be a member of the research group of Dr. P.K. Tandon, Associate Professor,
Department of Chemistry, University of Allahabad, Allahabad, and for their stimulating discussion as well as suggestions.
Funding from Council of Scientific & Industrial Research (CSIR), New Delhi (01/2538/11/EMR-II), India, is gratefully
acknowledged.

REFERENCES

[1] K. Hemalatha, G. Madhumitha, A. Kajbafvala, N. Anupama, R. Sompalle and S. M. Roopan, “Function of nanocatalyst in chemistry of
organic compounds revolution: An overview,” Hindawi Publishing Corporation, Journal of Nanomaterials, Volume 2013, Article ID
341015, 23 pages, http://dx.doi.org/10.1155/2013/341015
[2] P. T. Anastas and J. C. Warner, Green Chemistry: Theory and Practice, Oxford University Press: New York, 1998
[3] V. Polshettiwar and R. S. Varma, “Green chemistry by nano-catalysis,” Green Chem., vol. 12, pp. 743–754, 2010.
[4] M. B. Gawande, P. S. Brancoa and R. S. Varma, “Nano-magnetite (Fe3O4) as a support for recyclable catalysts in the development of
sustainable methodologies,” Chem. Soc. Rev., vol. 42, pp. 3371-3393, 2013.
[5] S. G. Babu and R. Karvembu, “Copper based nanoparticles-catalyzed organic transformations,” Catal. Surv. Asia, vol. 17, pp. 156-176,
2013.
[6] P. K. Tandon and S. B. Singh, “Catalytic applications of copper species in organic transformations: A review,” Journal of Catalyst and
Catalysis, vol. 1, pp. 1-14, 2014.
[7] K. Yan, G. Wu, T. Lafleur and C. Jarvis, “Production, properties and catalytic hydrogenation of furfural to fuel additives and value-
added chemicals,” Renewable and Sustainable Energy Reviews, vol. 38, pp. 663–676, 2014.
[8] K. Yan, G. Wu, C. Jarvis, J. Wen, and A. Chen, “Facile synthesis of porous microspheres composed of TiO2 nanorods with high
photocatalytic activity for hydrogen production,” Applied Catalysis B: Environmental, vol. 148, pp. 281–287, 2014.
[9] H. Luo, H. Jiang, T. Klande, Z. Cao, F. Liang, H. Wang, and J. Caro, “Novel cobalt-free, noble metal-free oxygen-permeable
40Pr0.6Sr0.4FeO3‑ δ−60Ce0.9Pr0.1O2−δ dual-phase membrane,” Chem. Mater, vol. 24, pp. 2148−2154, 2012.
[10] H. Luo, T. Klande, Z. Cao, F. Liang, H. Wang and J. Caro, “A CO2-stable reduction-tolerant Nd-containing dual phase membrane for
oxyfuel CO2 capture,” J. Mater. Chem. A, vol. 2, pp. 7780–7787, 2014.
[11] K. Yan, X. Wu, X. An, and X. Xie, “Facile synthesis and catalytic property of spinel ferrites by a template method,” Journal of Alloys
and Compounds, vol. 552, pp. 405–408, 2013.
[12] Y. Li and G. A. Somorjai, “Nanoscale advances in catalysis and energy applications,” Nano Lett., vol. 10, pp. 2289–2295, 2010.

- 112 -
Journal of Energy and Chemical Engineering Aug. 2014, Vol. 2 Iss. 3, PP. 106-115

[13] K. Yan, J. Liao, X. Wua and X. Xie, “A noble-metal free Cu-catalyst derived from hydrotalcite for highly efficient hydrogenation of
biomass-derived furfural and levulinic acid,” RSC Adv., vol. 3, pp. 3853-3856, 2013.
[14] H. Luo, H.Jiang, K. Efimov, J. Caro and H. Wang, “Influence of the preparation methods on the microstructure and oxygen
permeability of a CO2-stable dual phase membrane,” AIChE Journal, vol. 57, pp. 2738-2745, 2011.
[15] R. G. Chaudhuri and S. Paria, “Core/shell nanoparticles: Classes, properties, synthesis mechanisms, characterization, and applications,”
Chem. Rev., vol. 112, pp. 2373–2433, 2012.
[16] A. Roucoux and H. Patin, “Reduced transition metal colloids: a novel family of reusable catalysts?,” Chem. Rev., vol. 102, pp. 3757–
3778, 2002.
[17] B. L. Cushing, V. L. Kolesnichenko and C. J. O’Connor, “Recent advances in the liquid-phase syntheses of inorganic nanoparticles,”
Chem. Rev., vol. 104, pp. 3893–3946, 2004.
[18] J. Park, J. Joo, S.G. Kwon and T. Tyeon, “Synthesis of monodisperse spherical nanocrystals,” Angew. Chemie Int. Ed, vol. 46, pp.
4630–4660, 2007.
[19] K. Philippot and B. Chaudret, Organometallic derived metals, colloids and nanoparticles, in Comprehensive Organometallic Chemistry
III (Eds-in- Chief R.H. Crabtree and M.P. Mingos), Elsevier, pp. 71–99, 2007.
[20] G. U. Kulkarni, P. J. Thomas and C. N. R. Rao, “Mesoscopic assembly and other properties of metal and semiconductor nanocrystals,”
Chemistry of nanomaterials (eds C.N.R. Rao, A. Meuller, and A.K. Cheetham), pp. 58–93, 2004.
[21] W. Niu and G. Xu, “Crystallographic control of noble metal nanocrystals,” Nano Today, vol. 6, iss. 5, pp. 265–285, 2011.
[22] J. E. Mondloch, E. Bayram, and R.G. Finke, “A review of the kinetics and mechanisms of formation of supported nanoparticle
heterogeneous catalysts,” J. Mol. Catal. A: Chemical, vol. 355, iss. 1–38, 2012.
[23] C. Burda, X. Chen, R. Narayanan and M.A. El-Sayed, “Chemistry and properties of nanocrystals of different shapes,” Chem. Rev., vol.
105, iss. 4, pp.1025–1102, 2005.
[24] Y. M. Li and G. Somorjai, “Nanoscale advances in catalysis and energy applications,” Nano Lett., vol. 10, iss. 7, pp. 2289–2295, 2010.
[25] I. Nakamula, Y. Yamanoi, T. Imaok, K. Yamamoto, and H. Nishihara, “A uniform bimetallic rhodium/iron nanoparticle catalyst for the
hydrogenation of olefins and nitroarenes,” Angew. Chemie Int. Ed., vol. 50, iss. 26, pp. 5830–5833, 2011.
[26] W. Dingsheng and L. Yadong, “Bimetallic nanocrystals: liquid-phase synthesis and catalytic applications,” Adv. Mater., vol. 23, pp.
1044–1060, 2011.
[27] D. Astruc, F. Lu, and J. R. Aranzaes, “Nanoparticles as recyclable catalysts: a frontier field between homogeneous and heterogeneous
catalysis,” Angew. Chemie Int. Ed., vol. 44, pp. 7852–7872, 2005.
[28] S. Jansat, K. Pelzer, J. García-Anton, R. Raucoules, K. Philippot, A. Maisonnat, B. Chaudret, Y. Guari, A. Mehdi, C. Reye and R.J.P.
Corriu, “Synthesis of new Ru@SiO2 composite nanomaterials and their application as catalytic filters for selective gas detection,” Adv.
Funct. Mater, vol. 17, pp. 3339–3347, 2007.
[29] H.-P. Kormann, G. Schmid, K. Pelzer, K. Philippot and B. Chaudret, “Gas phase catalysis by metal nanoparticles in nanoporous
alumina membranes,” Z. Anorg. Allg. Chem., vol. 630, pp. 1913–1918, 2004.
[30] E. Castillejos, P.-J. Debouttiere L. Roiban, A. Solhy, V. Martinez, Y. Kihn, O. Ersen, K. Philippot, B. Chaudret, and P. Serp, “An
efficient strategy to drive nanoparticles into carbon nanotubes and the remarkable effect of confinement on their catalytic performance,
Angew,” Chemie Int. Ed., vol. 48, iss. 14, pp. 2529–2533, 2009.
[31] D. Rosario-Amorin, X. Wang, M. Gaboyard, R. Clerac, S. Nlate and K. Heuze, “Functionalized core-shell super-paramagnetic
nanoparticles: magnetically recoverable and reusable catalysts for Suzuki C-C cross coupling reactions,” Chem. Eur. J., vol. 15, pp.
12636–12643, 2009.
[32] K. Yan, T. Lafleur and J. Liao, “Facile synthesis of palladium nanoparticles supported on multi-walled carbon nanotube for efficient
hydrogenation of biomass-derived levulinic acid,” J Nanopart Res., vol. 15, p. 1906, 2013.
[33] Y. Qiao, H. Li, L. Hua, L. Orzechowski, K. Yan, B. Feng, Z. Pan, N. Theyssen, W. Leitner and Z. Hou, “Peroxometalates immobilized
on magnetically recoverable catalysts for epoxidation,” ChemPlusChem., vol. 77, pp. 1128 – 1138, 2012.
[34] K. Yan, C. Jarvis, T. Lafleur, Y. Qiao, and X. Xie, “Novel synthesis of Pd nanoparticles for hydrogenation of biomass-derived platform
chemicals showing enhanced catalytic performance,” RSC Adv., vol. 3, pp. 25865-25871, 2013.
[35] Z. Cao, H. Jiang, H. Luo, S. Baumann, W. A. Meulenberg, H. Voss and J. Caro, “Simultaneous overcome of the equilibrium limitations
in BSCF oxygen-permeable membrane reactors: Water splitting and methane coupling,” Catalysis Today, vol. 193, pp. 2–7, 2012.
[36] K. Yan, T. Lafleur, G. Wu, J. Liao, C. Ceng and X. Xie, “Highly selective production of value-added γ-valerolactone from biomass-
derived levulinic acid using the robust Pd nanoparticles,” Applied Catalysis A: General, vol. 468, pp. 52–58, 2013.
[37] K. Yan, G. Wu, J. Wen and A. Chen, “One-step synthesis of mesoporous H4SiW12O40-SiO2 catalysts for the production of methyl and
ethyl levulinate biodiesel,” Catalysis Communications, vol. 34, pp. 58–63, 2013.
[38] S. L. Candelaria, Y. Shao, W. Zhou, X. Li, J. Xiao, J.-G. Zhang, Y. Wang, J. Liu, J. Li, G. Cao, “Nanostructured carbon for energy
storage and conversion,” Nano Energy, vol. 1, pp. 195–220, 2012.
[39] K. Yan and A. Chen, “Efficient hydrogenation of biomass-derived furfural and levulinic acid on the facilely synthesized noble-metal-
free Cu–Cr catalyst,” Energy, vol. 58, pp. 357–363, 2013.
[40] H. Luo, T. Klimczuk, L. Müchler, L. Schoop, D. Hirai, M. K. Fuccillo, C. Felser, and R. J. Cava, “Superconductivity in the Cu(Ir1-
xPtx)2Se4 spinel,” Phys. Rev. B, vol. 87, 214510, 2013.
[41] K. Yan, T. Lafleur C. Jarvis and G. Wu, “Clean and selective production of у-valerolactone from biomass-derived levulinic acid
catalyzed by recyclable Pd nanoparticle catalyst,” Journal of Cleaner Production, vol. 72, pp. 230-232, 2014.
[42] B. R. Cuenya, “Synthesis and catalytic properties of metal nanoparticles: Size, shape, support, composition, and oxidation state effects,”

- 113 -
Journal of Energy and Chemical Engineering Aug. 2014, Vol. 2 Iss. 3, PP. 106-115

Thin Solid Films, vol. 518, pp. 3127–3150, 2010.

[43] C. Q. Sun, “Size dependence of nanostructures: Impact of bond order deficiency,: Prog. Solid State Chem., vol. 35, iss. 1, pp. 1–159,
2007.
[44] L. Pan, M. Gu, G. Ouyang and C.Q. Sun, “Behind the quantum and size effects: Broken-bond-induced local strain and skin-depth
densified quantum trapping of charge and energy,” Key Eng. Mater., vol. 444, pp. 17–45, 2010.
[45] K. Yan and A. Chen, “Selective hydrogenation of furfural and levulinic acid to biofuels on the ecofriendly Cu–Fe catalyst,” Fuel, vol.
115, pp. 101–108, 2014.
[46] A. J. Gellman and N. Shukla, “Nanocatalysis: More than speed,” Nature Materials, vol. 8, pp. 87-88, 2009.
[47] B. C. Gates, “Catalysis: Induvidual nanoparticles in action,” Nature Nanotechnology, vol. 3, pp. 583-584, 2008.
[48] J. A. Gladysz, “Introduction:  Recoverable catalysts and reagents perspective and prospective,” Chem. Rev., vol. 102, pp. 3215-3216,
2002.
[49] B. Hvolbæk, T. V. W. Janssens, B. S. Clausen, H. Falsig, C. H. Christensen, and J. K. Nørskov, “Catalytic activity of Au nanoparticles,”
Nanotoday, vol. 2, iss. 4, pp. 14-18, 2007.
[50] Y. Bia and G. Lua, “Nano-Cu catalyze hydrogen production from formaldehyde solution at room temperature,” International Journal of
Hydrogen Energy, vol. 33, pp. 2225–2232, 2008.
[51] V. Nagpal, A.D. Bokare, R. C. Chikate, C. V. Rode, and K. M. Paknikar, “Reductive dechlorination of -hexachlorocyclohexane using
Fe–Pd bimetallic nanoparticles,” Journal of Hazardous Materials, vol. 175, pp. 680–687, 2010.
[52] Y.-H. Tee, L. Bachas, and D. Bhattacharya, “Degradation of trichloroethylene and dichlorobiphenyls by iron-based bimetallic
nanoparticles,” J. Phys. Chem. C, vol. 113, pp. 9454–9464, 2009.
[53] J.M. Liu, X.G. Peng, W. Sun, Y.W. Zhao and C.G. Xia, Magnetically separable Pd catalyst for carbonylative sonogashira coupling
reactions for the synthesis of α,β-alkynyl ketones. Org. Lett., 10, 3933–3936, 2008.
[54] M. B. Gawande, A. K. Rathi, P. S. Branco, I. D. Nogueira, A. Velhinho, J. J. Shrikhande, U. U. Indulkar, R. V. Jayaram, C. A. A.
Ghumman, N. Bundaleski, and O .M. N. D. Teodoro, “Regio- and chemoselective reduction of nitroarenes and carbonyl compounds
over recyclable magnetic ferrite[BOND]nickel nanoparticles (Fe3O4[BOND]Ni) by using glycerol as a hydrogen source,” Chem.–Eur.
J., vol. 18, pp. 12628–12632, 2012.
[55] M. B. Gawande, A. Rathi, I. D. Nogueira, C. A. A. Ghumman, N. Bundaleski, O. M. N. D. Teodoro and P.S. Branco, “A Recyclable
ferrite–Co magnetic nanocatalyst for the oxidation of alcohols to carbonyl compounds,” ChemPlusChem, vol. 77, pp. 865–871, 2012.
[56] M. J. Aliaga, D. J. Ramon and M. Yus, “Impregnated copper on magnetite: an efficient and green catalyst for the multicomponent
preparation of propargylamines under solvent free conditions,” Org. Biomol. Chem., vol. 8, pp. 43–46, 2010.
[57] A. Noujima, T. Mitsudome, T. Mizugaki, K. Jitsukawa and K. Kaneda, “Gold nanoparticle-catalyzed environmentally benign
deoxygenation of epoxides to alkenes,” Molecules, vol. 16, pp. 8209-8227, 2011.
[58] M. Boominathan, N. Pugazhenthiran, M. Nagaraj, S. Muthusubramanian, S. Murugesan and N. Bhuvanesh, “Nanoporous titania-
supported gold nanoparticle-catalyzed green, synthesis of 1,2,3-triazoles in aqueous medium,” ACS Sustainable Chem. Eng., vol. 1,
1405−1411, 2013.
[59] A. Imtiaz, M. A. Farrukh, M. K.-ur-rahman and R. Adnan, “Micelle-assisted synthesis of Al2O3•CaO nanocatalyst: Optical properties
and their applications in photodegradation of 2,4,6-trinitrophenol,” The Scientific World Journal, Volume 2013,
http://dx.doi.org/10.1155/2013/641420, 2013. The Scientific World Journal
[60] J. Safaei-Ghomi, M. A. Ghasemzadeha, and M. Mehrabi, “Calcium oxide nanoparticles catalyzed one-step multicomponent synthesis of
highly substituted pyridines in aqueous ethanol media,” Scientia Iranica C, vol. 20, iss. 3, pp. 549–554, 2013.
[61] A. Balanta, C. Godard, and C. Claver, “Pd nanoparticles for C–C coupling reactions,” Chem. Soc. Rev., vol. 40, pp. 4973–4985, 2011.
[62] D. Srimani, A. Bej and A. Sarkar, “Palladium nanoparticle catalyzed Hiyama coupling reaction of benzyl halides,” J. Org. Chem., vol.
iss. 75, pp. 4296–4299, 2010.
[63] P. K. Tandon, S. B. Singh and M. Srivastava, “Synthesis of some aromatic aldehydes and acids by sodium ferrate in presence of copper
nano-particles adsorbed on K 10 montmorillonite using microwave irradiation,” Appl. Organometal. Chem., vol. 21, pp. 264–267, 2007.
[64] H.-J. Xu, Y.-F. Liang, Z.-Y. Cai, H.-X. Qi, C.-Y. Yang and Y.-S. Feng, “CuI-Nanoparticles-catalyzed selective synthesis of phenols,
anilines, and thiophenols from aryl halides in aqueous solution,” J. Org. Chem., vol. 76, pp. 2296–2300, 2011.
[65] S. U. Tekale, S. S. Kauthale, K. M. Jadhav, and R. P. Pawar, “Nano-ZnO catalyzed green and efficient one-pot four-component
synthesis of pyranopyrazoles,” Hindawi Publishing Corporation, Journal of Chemistry, Volume 2013, Article ID 840954, 8 pages,
http://dx.doi.org/10.1155/2013/840954
[66] B.V. Kumar, H.S.B. Naik, D. Girija and B.V. Kumar, “ZnO nanoparticle as catalyst for efficient green one-pot synthesis of coumarins
through Knoevenagel condensation,” J. Chem. Sci., vol. 123, iss. 5, pp. 615–621, 2011.
[67] J. S.-Ghomi and M. A. Ghasemzadeh, “Silver iodide nanoparticle as an efficient and reusable catalyst for the one-pot synthesis of
benzofurans under aqueous conditions,” J. Chem. Sci., vol. 125, iss. 5, pp. 1003–1008, 2013.
[68] H. Cong, C. F. Becker, S. J. Elliott, M. W. Grinstaff and J. A. Porco, Jr., “Silver nanoparticle-catalyzed Diels-Alder cycloadditions of 2-
hydroxychalcones,” J. Am. Chem. Soc., vol. 132, pp. 7514–7518, 2010.
[69] S. B. Kalidindi and B. R. Jagirdar, “Nanocatalysis and prospects of green chemistry,” ChemSusChem, vol. 5, iss. 1, pp. 65–75, 2012.
[70] B. Zhou, R. Balee, and R. Groenendaal, “Nanoparticle and nanostructure catalysts: technologies and markets,” Nanotechnology Law &
Business, vol. 2, iss. 3, pp. 222–229, 2005.
[71] M. Haruta, N. Yamada, T. Kobayashi, and S. Lijima, “Gold catalysts prepared by co-precipitation for low temperature oxidation of
hydrogen and of carbon monoxide,” J. Catal., vol. 115, pp. 301-309, 1989.

- 114 -
Journal of Energy and Chemical Engineering Aug. 2014, Vol. 2 Iss. 3, PP. 106-115

[72] M. Z¨ach, C. H¨agglund, D. Chakarov, and B. Kasemo, “Nanoscience and nanotechnology for advanced energy systems,” Current
Opinion in Solid State and Materials Science, vol. 10, iss. 3-4, pp. 132–143, 2006.
[73] M. Zahmakiran and S. Ozkar, “Metal nanoparticles in liquid phase catalysis; from recent advances to future goals,” Nanoscale, vol. 3,
iss. 9, pp. 3462–3481, 2011.
[74] J. M. Campelo, D. Luna, R. Luque, J. M. Marinas, and A.A. Romero, “Sustainable preparation of supported metal nanoparticles and
their applications in catalysis,” ChemSusChem, vol. 2, iss. 1, pp. 18–45, 2009.
[75] W. Teunissen, A. A. Bol, and J.W. Geus, “Magnetic catalyst bodies,” Catalysis Today, vol. 48, iss. 1–4, pp. 329–336, 1999.

- 115 -

View publication stats