Applications of Nano-Catalyst in New Era: Journal of Saudi Chemical Society

Journal of Saudi Chemical Society (2012) 16, 307–325
King Saud University
Journal of Saudi Chemical Society

www.ksu.edu.sa
www.sciencedirect.com
ORIGINAL ARTICLE
Applications of nano-catalyst in new era

Shalini Chaturvedi a, Pragnesh N. Dave a,*
, N.K. Shah b
a
Department of Chemistry, Kachchh University, Kachchh 370001, India
b
Department of Chemistry, School of Science, Gujarat University, Ahmedabad 380009, India
Received 27 September 2010; accepted 30 January 2011

Available online 4 March 2011
KEYWORDS Abstract In the era of nanoscience where all the devices and technologies are going to smaller and
Nanoscience; smaller in size with improved properties; catalysis is an important field of application. In this review
Nanomaterials; article we are trying to summarize data reported in literature for application of nano sized catalyst
Nanocatalyst; in our daily life which are useful for human beings. Improvement in catalytic properties due size of
Carbon nanotube catalyst reduced to nano scale is discussed here. Introductive points regarding nanoscience; their
functional approaches; current research are also here.
Main applications of nanocatalysts in water purification; fuel cell; energy storage; in composite
solid rocket propellants; bio diesel production; in medicine; in dye; application of carbon nano
tubes and several other point of application are discussed here in detail.
ª 2011 King Saud University. Production and hosting by Elsevier B.V. All rights reserved.
1. Introduction and the smallest structures we will ever make will have the
dimensions of a few nanometers. This is because as soon as
Nanoscience is the study of phenomena on a nanometer scale. a few atoms are placed next to each other, the resulting struc-
Atoms are a few tenths of a nanometer in diameter and mole- ture is a few nanometers in size. The smallest transistors, mem-
cules are typically a few nanometers in size. The smallest struc- ory elements, light sources, motors, sensors, lasers, and pumps
tures humans have made have dimensions of a few nanometers are all just a few nanometers in size like carbon nanotubes,
grapheme etc.
* Corresponding author. Tel.: +91 02832235002. Carbon nanotubes (CNTs) have exceptional mechanical
E-mail addresses: [email protected], pragnesh7@yahoo. properties, particularly high tensile strength and light weight.
com (P.N. Dave). An obvious area of application would be in nanotube rein-
forced composites, with performance beyond current carbon-
1319-6103 ª 2011 King Saud University. Production and hosting by
fiber composites. One current limit to the introduction of
Elsevier B.V. All rights reserved.
CNTs in composite is the problem of structuring the tangle
Peer review under responsibility of King Saud University. of nanotubes in a well-ordered manner so that use can be made
doi:10.1016/j.jscs.2011.01.015 of their strength. Another challenge is generating strong bond-
ing between CNTs and the matrix, to give good overall com-
posite performance and retention during wear or erosion of
Production and hosting by Elsevier composites. The surfaces of CNTs are smooth and relatively
unreactive and so tend to slip through the matrix when it is
308 S. Chaturvedi et al.
stressed. One approach that is being explored to prevent this 1 GB of information in DNA. They self reproduce. They con-
slippage is the attachment of chemical side-groups to CNTs, struct tough and strong material. Biology is an important
effectively to form ‘anchors’. Another limiting factor is the cost source for inspiration in nanotechnology. Copying engineering
of production of CNTs. However, the potential benefits of principles from biology and applying it to create new materials
such light, high strength material in numerous applications and technologies is called biomimetics.
for transportation are such that significant further research is Nanomedicine is the medical application of nanotechnol-
likely (Bakunin et al., 2004; Edelstein and Cammarata, 1998). ogy. Nanomedicine ranges from the medical applications of
Graphene is an allotrope of carbon, whose structure is one- nanomaterials, to nanoelectronic biosensors, and even possible
atom-thick planar sheets of sp2-bonded carbon atoms that are future applications of molecular nanotechnology. Current
densely packed in a honeycomb crystal lattice. Graphene is most problems for nanomedicine involve understanding the issues
easily visualized as an atomic-scale chicken wire made of carbon related to toxicity and environmental impact of nanoscale
atoms and their bonds. The crystalline or ‘‘flake’’ form of graph- materials.
ite consists of many graphene sheets stacked together.
The carbon–carbon bond length in graphene is about 1.1. Nanomaterials
0.142 nanometers. Graphene sheets stack to form graphite
with an interplanar spacing of 0.335 nm, which means that a Nanomaterials are those which have structured components
stack of 3 million sheets would be only one millimeter thick. with at least one dimension less than 100 nm. Materials that
Graphene is the basic structural element of some carbon allo- have one dimension in the nanoscale (and are extended in the
tropes including graphite, charcoal, carbon nanotubes and ful- other two dimensions) are layers, such as a thin films or surface
lerenes. It can also be considered as an indefinitely large coatings. Some of the features of computer chips come in this
aromatic molecule, the limiting case of the family of flat poly- category. Materials that are nanoscale in two dimensions
cyclic aromatic hydrocarbons. The Nobel Prize in Physics for (and extended in one dimension) include nanowires and nano-
2010 was awarded to Andre Geim and Konstantin Novoselov tubes. Materials that are nanoscale in three dimensions are par-
‘‘for groundbreaking experiments regarding the two- ticles, for example precipitates, colloids and quantum dots (tiny
dimensional material graphene’’. particles of semiconductor materials). Nanocrystalline materi-
Besides the technological relevance of nanoscience (or per- als, made up of nanometer-sized grains, also fall into this cate-
haps because of the technological relevance) there is an enor- gory. Some of these materials have been available for some
mous hype associated with it. Fantastic claims have been time; others are genuinely new (Taniguchi, 1974; Lubick and
made about faster computers, cheap production of goods, Betts, 2008; Edelstein and Cammarata, 1998).
and medical breakthroughs. Nanotechnology is expected to Two principal factors cause the properties of nanomaterials
appear in products such as tennis rackets, self-cleaning cars, to differ significantly from other materials: increased relative
paint, food, and cosmetics. surface area, and quantum effects. These factors can change
It’s a small, small, small, small world: Manufactured prod- or enhance properties such as reactivity, strength and electrical
ucts are made from atoms. The properties of those products characteristics. As a particle decreases in size, a greater propor-
depend on how those atoms are arranged. If we rearrange tion of atoms are found at the surface compared to those in-
the atoms in coal, we get diamonds. If we rearrange the atoms side. For example, a particle of size 30 nm has 5% of its
in sand (and add a pinch of impurities) we get computer chips. atoms on its surface, at 10 nm 20% of its atoms, and at
If we rearrange the atoms in dirt, water and air we get grass. 3 nm 50% of its atoms. Thus nanoparticles have a much great-
Nanoscience in physics, chemistry, biology, and medicine: er surface area per unit mass compared with larger particles.
Physics is the mother of the natural sciences. In principle, As growth and catalytic chemical reactions occur at surfaces,
physics can be used to explain everything that goes on at the this means that a given mass of material in nanoparticulate
nanoscale. There is active physics research going on in nanome- form will be much more reactive than the same mass of mate-
chanics, quantum computation, quantum teleportation, and rial made up of larger particles (Taniguchi, 1974; Lubick and
artificial atoms. While physics can explain everything, some- Betts, 2008; Edelstein and Cammarata, 1998).
times it is more convenient to think of nanostructures in terms
of chemistry where the molecular interactions are described in 1.2. Fundamental concepts
terms of bonds and electron affinities.
Chemistry is the study of molecules and their reactions with One nanometer (nm) is one billionth, or 109 of a meter. By
each other. Since molecules typically have dimensions of a few comparison, typical carbon–carbon bond lengths, or the spac-
nanometers, almost all of nanoscience can be reduced to ing between these atoms in a molecule, are in the range 0.12–
chemistry. Chemistry research in nanotechnology concerns 0.15 nm, and a DNA double-helix has a diameter around
C60 molecules, carbon nanotubes, self-assembly, structures 2 nm. On the other hand, the smallest cellular life-forms, the
built using DNA, and supermolecular chemistry. Sometimes bacteria of the genus Mycoplasma, are around 200 nm in
the chemical description of a nanostructure is insufficient to length. To put that scale in another context, the comparative
describe its function. For instance, a virus can be described size of a nanometer to a meter is the same as that of a marble
best in terms of biology. to the size of the earth.
Biology is sometimes described as nanotechnology that Two main approaches are used in nanotechnology. In the
works. Biological systems contain small and efficient motors. ‘‘bottom-up’’ approach, materials and devices are built from
There are more than 50 kinds of motors found in cells. Biolog- molecular components which assemble themselves chemically
ical systems produce impressive control systems. The brain of a by principles of molecular recognition. In the ‘‘top-down’’
bee is tiny and consumes little power yet regulates complex approach, nano-objects are constructed from larger entities
flying behavioral patterns. A cell one micron in size can store without atomic-level control.
Applications of nano-catalyst in new era 309
Larger to smaller: a materials perspective: A number of is a term given to the concept of engineered nanosystems
physical phenomena become pronounced as the size of the sys- (nanoscale machines) operating on the molecular scale. It is
tem decreases. These include statistical, mechanical effects, as especially associated with the concept of a molecular assem-
well as quantum mechanical effects, for example the ‘‘quantum bler, a machine that can produce a desired structure or device
size effect’’ where the electronic properties of solids are altered atom-by-atom using the principles of mechano-synthesis.
with great reductions in particle size. This effect does not come Manufacturing in the context of productive nanosystems is
into play by going from macro to micro dimensions. However, not related to, and should be clearly distinguished from, the
it becomes dominant when the nanometer size range is conventional technologies used to manufacture nanomaterials
reached. Additionally, a number of physical (mechanical, elec- such as carbon nanotubes, nanoparticles (Lubick and Betts,
trical, optical, etc.) properties change when compared to mac- 2008), molecular wire or nanowires (Mihailovic, 2009) and
roscopic systems. One example is the increase in surface area to Switches (Emberly and Kriczenow, 2003). Molecular wires
volume ratio altering mechanical, thermal and catalytic prop- (or sometimes called molecular nanowires) are molecular-scale
erties of materials. Diffusion and reactions at nanoscale, nano- objects which conduct electrical current. They are the funda-
structures materials and nanodevices with fast ion transport mental building blocks for molecular electronic devices. Their
are generally referred to nanoionics. Novel mechanical proper- typical diameters are less than three nanometers, while their
ties of nanosystems are of interest in the nanomechanics re- bulk lengths may be macroscopic, extending to centimeters
search. The catalytic activity of nanomaterials also opens or more.
potential risks in their interaction with biomaterials (Lubick When the term ‘‘nanotechnology’’ was independently
and Betts, 2008). coined and popularized by Eric Drexler (who at the time
Materials reduced to the nanoscale can show different was unaware of an earlier usage by Norio Taniguchi) it re-
properties compared to what they exhibit on a macroscale, en- ferred to a future manufacturing technology based on molec-
abling unique applications. For instance, opaque substances ular machine systems. The premise was that molecular scale
become transparent (copper); stable materials turn combusti- biological analogies of traditional machine components dem-
ble (aluminum); solids turn into liquids at room temperature onstrated molecular machines were possible: by the countless
(gold); insulators become conductors (silicon). A material such examples found in biology, it is known that sophisticated, sto-
as gold, which is chemically inert at normal scales, can serve as chastically optimized biological machines can be produced
a potent chemical catalyst at nanoscales. Much of the fascina- (Edelstein and Cammarata, 1998). It is hoped that develop-
tion with nanotechnology stems from these quantum and sur- ments in nanotechnology will make possible their construction
face phenomena that matter exhibits at the nanoscale (Lubick by some other means, perhaps using biomimetic principles.
and Betts, 2008). However, Drexler and other researchers have proposed that
Simple to complex: a molecular perspective: Modern syn- advanced nanotechnology, although perhaps initially imple-
thetic chemistry has reached the point where it is possible mented by biomimetic means, ultimately could be based on
to prepare small molecules to almost any structure. These mechanical engineering principles, namely, a manufacturing
methods are used today to produce a wide variety of useful technology based on the mechanical functionality of these
chemicals such as pharmaceuticals or commercial polymers. components (such as gears, bearings, motors, and structural
These approaches utilize the concepts of molecular self- members) that would enable programmable, positional assem-
assembly and/or supramolecular chemistry to automatically bly to atomic specification. In general it is very difficult to
arrange themselves into some useful conformation through assemble devices on the atomic scale, as all one has to position
a bottom-up approach. The concept of molecular recognition atoms are other atoms of comparable size and stickiness
is especially important: molecules can be designed so that a (Edelstein and Cammarata, 1998).
specific conformation or arrangement is favored due to Current research: This includes subfields which develop or
non-covalent intermolecular forces. The Watson–Crick base study materials having unique properties arising from their
pairing rules are a direct result of this, as is the specificity nanoscale dimensions (Das et al., 2007):
of an enzyme being targeted to a single substrate, or the spe-
cific folding of the protein itself. Thus, two or more compo- Interface and colloid science has given rise to many materi-
nents can be designed to be complementary and mutually als which may be useful in nanotechnology, such as carbon
attractive so that they make a more complex and useful nanotubes and other fullerenes, and various nanoparticles
whole (Taniguchi, 1974; Edelstein and Cammarata, 1998). and nanorods.
Such bottom-up approaches should be able to produce Nanoscale materials can also be used for bulk applications;
devices in parallel and much cheaper than top-down meth- most present commercial applications of nanotechnology
ods, but could potentially be overwhelmed as the size and are of this flavor.
complexity of the desired assembly increases. Most useful Progress has been made in using these materials for medical
structures require complex and thermodynamically unlikely applications.
arrangements of atoms. Nevertheless, there are many exam- Nanoscale materials are sometimes used in solar cells which
ples of self-assembly based on molecular recognition in biol- combats the cost of traditional silicon solar cells.
ogy, most notably Watson–Crick base pairing and enzyme–
substrate interactions. The challenge for nanotechnology is Bottom-up approaches: These seek to arrange smaller com-
whether these principles can be used to engineer novel con- ponents into more complex assemblies:
structs in addition to natural ones (Levins and Schafmeister,
2005). DNA nanotechnology utilizes the specificity of Watson–
Molecular nanotechnology: a long-term view: Molecular Crick base pairing to construct well-defined structures out
nanotechnology, sometimes called molecular manufacturing, of DNA and other nucleic acids.
Approaches from the field of ‘‘classical’’ chemical synthesis Recent progress in synthesis of nanomaterials has made it
also aim at designing molecules with well-defined shape possible to fabricate nanometer-sized materials with controlled
(e.g., bis-peptides) (Lu and Schüth, 2006). structures and functionalities (Lee et al., 2009; Ko and Jang,
More generally, molecular self-assembly seeks to use con- 2006; Yoon et al., 2007; Choi et al., 2007). In particular, versa-
cepts of supramolecular chemistry, and molecular recogni- tile porous materials with nanometer feature sizes have
tion in particular, to cause single-molecule components to emerged as promising candidates for applications in the fields
automatically arrange themselves into some useful of catalysis (Ko and Jang, 2006; Yoon et al., 2007; Choi et al.,
conformation. 2007), energy conversion and storage (Moon et al., 2005; Choi
The assembly of nanoparticles of two different materials and Jang, 2008), separation (Giri et al., 2005), and biomedical
into a binary nanoparticle superlattice is a promising way science (Yang et al., 2007; Guo et al., 2009; Oh et al., 2010).
of synthesizing a large variety of materials (metamaterials)
with precisely controlled chemical composition and tight 1.3. Properties of nanomaterials
placement of the components. In theory only a few stable
binary superlattice structures can assemble from hard In tandem with surface-area effects, quantum effects can begin
spheres, potentially limiting this approach. But all is not to dominate the properties of matter as size is reduced to the
lost because at the nanometer scale there are additional nanoscale. These can affect the optical, electrical and magnetic
forces (electrostatic, van der Waals and dipolar) that can behavior of materials, particularly as the structure or particle
stabilize binary nanoparticulate structures. There are sev- size approaches the smaller end of the nanoscale. Materials
eral methods of synthesis of a dozen novel structures from that exploit these effects include quantum dots and quantum
various combinations of metal, semiconductor, magnetic well lasers for optoelectronics.
and dielectric nanoparticles. This demonstrates the poten- For other materials such as crystalline solids, as the size of
tial of self-assembly in designing families of novel materials their structural components decreases, there is much greater
and metamaterials with programmable physical and chem- interface area within the material; this can greatly affect both
ical properties. mechanical and electrical properties. For example, most metals
are made up of small crystalline grains; the boundaries be-
Top-down approaches: These seek to create smaller devices tween the grain slow down or arrest the propagation of defects
by using larger ones to direct their assembly: when the material is stressed, thus giving it strength. If these
grains can be made very small, or even nanoscale in size, the
Many technologies descended from conventional solid-state interface area within the material greatly increases, which en-
silicon methods for fabricating microprocessors are now hances its strength. For example, nanocrystalline nickel is as
capable of creating features smaller than 100 nm, falling strong as hardened steel (Edelstein and Cammarata, 1998).
under the definition of nanotechnology. Giant magnetore-
sistance-based hard drives already on the market fit this
description, as do atomic layer deposition (ALD) tech- 2. Nanocatalyst: effect of size reduction
niques. Peter Grünberg and Albert Fert received the Nobel
Prize in Physics for their discovery of Giant magnetoresis- Catalytic technologies are critical to present and future energy,
tance and contributions to the field of spintronics in chemical process, and environmental industries. Conversion of
2007. crude oil, coal and natural gas to fuels and chemical feedstock,
Solid-state techniques can also be used to create devices production of a variety of petrochemical and chemical prod-
known as nano electromechanical systems, which are ucts, and emission control of CO, hydrocarbons, and NO,
related to micro electromechanical systems. all rely on catalytic technologies. Catalysts are also essential
Atomic force microscope tips can be used as a nanoscale components of electrodes for fuel cells that use either solid
‘‘write head’’ to deposit a chemical upon a surface in a oxide ionic or polymeric proton electrolyte. Drivers for devel-
desired pattern in a process called dip pen nanolithography. opment of advanced catalysts include (i) production of high
This fits into the larger subfield of nanolithography. value products with inexpensive raw materials, (ii) energy-
efficient and environmentally-benign chemical conversion pro-
Focused ion beams can directly remove material, or even cesses, (iii) increasingly stringent environmental regulations,
deposit material when suitable pre-cursor gasses are applied and (iv) low-cost catalysts such as with reduction or replace-
at the same time. For example, this technique is used routinely ment of precious metals (Liu, 2005).
to create sub-100 nm sections of material for analysis in trans- In catalysis, chemical reactions in solid, gases or liquids are
mission electron microscopy. accelerated by introducing a solid phase that ideally contains
Functional approaches: These seek to develop components large enough amounts of the right kind of site for chemical
of a desired functionality without regard to how they might reactants to adsorb, react, and desorbs. Because optimization
be assembled: of the catalyst requires increasing the numbers of sites to ex-
pand surface area, the catalytic particle size must be decreased.
Molecular electronics seeks to develop molecules with use- In contemporary laboratories, active catalysts tend to consist
ful electronic properties. These could then be used as sin- of carefully prepared nanometer-sized particles on supports
gle-molecule components in a nanoelectronic device (Jang, with nanometer-sized pores or structural features. Modern cat-
2006). alysts typically consist of multiple-component active phases
Synthetic chemical methods can also be used to create what that may include a support tailored to disperse, isolate, or
forensics call synthetic molecular motors, such as in a so- otherwise enhance the structure or properties of individual cat-
called nano car. alytic particles. One goal of catalysis research is to understand
how decreasing the size of catalytic particles alters the intrinsic they are highly porous, light, stable, and non-expensive. Their
catalytic performance beyond simply expanding surface area. unique tubular structure is favorable for hydrogen uptake
A corollary goal is learning how to design and prepare cata- (Darkrim et al., 2002). Hydrogen, owing to its high energy
lysts with the most effective size and structure. content and non-polluting nature, is considered as an ideal en-
The exciting prospect of nanoscience is its potential use in ergy carrier which may be widely utilized in the near future
almost any conceivable domain. Every field from medicine (Züttel, 2004; Shi and Hwang, 2007). According to the litera-
and electronics to manufacturing and fashion stand to benefit ture (Fazle Kibria et al., 2001), the material characteristics of
from advances in nanotechnology. And while nano-scale tech- CNTs, governed by preparation procedures, significantly af-
nology is multifaceted in its application, the use of nanocrys- fect their hydrogen storage capability. Chang et al. (2008) stud-
tals as catalysts is perhaps the most intriguing. The key ied, a novel NCMs preparation method utilizing the Metal
concept to understanding nanocrystal catalysis involves the ra- Dusting (MD) process which is developed. Moreover, the pos-
tio of surface area and volume. As an object gets larger, its sur- sibility of using the produced CNTs as a hydrogen storage
face area increases less in relation to its volume. Therefore, material, which has not been explored in the literature. The ef-
smaller objects have more surface area with respect to their fects of acid post-treatment on the microstructure and hydro-
volume. This has important implications for chemical reac- gen storage performance of the CNTs are also evaluated. The
tions. High surface area-to volume ratios are favorable for as-prepared multi-wall CNTs produced at 600 C show a
chemical reactions. Going back to the campfire example, kind- hydrogen discharge capacity of 57 mAh/g; which was mea-
ling is used to start the fire. The small pieces of wood have a sured; using an electrochemical method under room tempera-
greater surface area with respect to their volume than larger ture and pressure. It was found that the post acid treatment
logs. Lighting the kindling therefore results in a quicker com- in boiling nitric acid solution for 4 h can effectively remove
bustion. Additionally, if one throws a handful of sawdust onto metal particles and deposited amorphous carbon from the
a burning fire, a giant flare results. This reaction is chemically as-prepared CNTs. As a result, the hydrogen discharge
identical to ordinary wood burning, but it occurs at a much capacity can be significantly increased to 104 mAh/g. How-
faster rate. The general purpose of catalysts is to increase the ever, further prolonging the etching time not only decreases
speed of a given reaction. This is achieved through kinetic the crystallinity but also damages the tubular structure of
means and does not directly affect the thermodynamic proper- the CNTs, degrading the hydrogen storage performance.
ties of a chemical system. Introducing a catalyst increases the The experimental results indicate that MD-produced NCMs
speed of a reaction in one of three ways; it can lower the acti- are potential candidates for use as hydrogen storage materials.
vation energy for the reaction, act as a facilitator and bring the
reactive species together more effectively, or create a higher 3.2. Water purification
yield of one species when two or more products are formed.
Depending on the application, nano-catalysts can be used in Hydrogen is the latest in the succession of energy providers,
all the ways listed above. Nano-materials are more effective with many social, economic, and environmental benefits to
than conventional catalysts for two reasons. First, their extre- its credit including its utilization in chemical industries which
mely small size (typically 10–80 nm) yields a tremendous accounts for 40% of its consumption. This implicates the pre-
surface area-to-volume ratio. Also, when materials are fabri- ciousness of H2 and its high demand to the world today and
cated on the nanoscale, they achieve properties not found tomorrow. Considerable amounts of hydrogen is being con-
within their macroscopic counterparts. Both of these reasons sumed in the various reduction processes, namely reduction
account for the versatility and effectiveness of nanocatalysts. of metal catalysts that are employed for various hydrogenation
and other reactions apart from its usage in the hydrogenation
reactions itself. Thus, preparation methods that can produce
3. Applications of nanocatalysts catalysts directly in metallic form without employing any
hydrogen for bringing the oxidic or other forms of catalysts
In era of nanotechnology where size of every object is going to to their metallic forms can be highly advantageous in reducing
smaller and smaller with their enhanced properties; catalysts of hydrogen consumption. Shashikala et al. (2007) reported that
nano size are also used in several chemical processes and ben- the process of maintaining hydrogen economy by synthesizing
eficial for human being. In this section we are trying to collect nano-metallic particles of silver employing novel electro-chem-
all literature data on application of nanocatalyst reported ical deposition method over carbon covered alumina support.
within the last few years. This method gives a silver catalyst, which is highly efficient in
controlling microbes in water. It is also concluded evidently
3.1. Carbon nanotubes that the Ag supported catalysts are reusable. The combined
characteristics of Al2O3 and carbon like low acidity, high
Nano-sized carbon materials (NCMs), especially carbon nano- mechanical strength and presence of meso pores in carbon cov-
tubes (CNTs) have attracted a lot of attention because of their erage in alumina (CCA) are also helpful for designing highly
unique physical and mechanical properties (Saito et al., 1993; active AgCCA catalyst.
Ruoff and Lorents, 1995). CNTs have been used in many fields Liu et al. (2004) studied the use of visible light sensitive
as field emission sources (Trans et al., 1998), electric nano-con- N-doped TiO2 and ZrO2 nanoparticles to achieve significant
ductors (Mintmire et al., 1992), Li ion secondary batteries improvements in biofilm and Escherichia coli bacteria photo-
(Maurin et al., 1999), electric double-layer capacitors (Frac- degradation efficiency. Result shows that the different nitrogen
kowiak et al., 2000), fuel cells (Bessel et al., 2001), and molec- sources yield TiO2xNx with different photocatalytic perfor-
ular sieves (Wang et al., 1999). In addition, CNTs have been mance, which could be explained by the different binding sites
recently used to adsorb hydrogen (Dillon et al., 1997) since of N dopants in a given metal oxide matrix. The abatement of
E. coli and biofilm bacteria without extracellular polymeric can be improved by achieving nanosized particles, uniform dis-
substance (EPS) showed distinctive kinetic patterns indicating tribution and high loading of catalysts over large surface area
the complexity of bactericidal degradation. Removing the carbons (Wilsn and Gottesfeld, 1992; Liu et al., 2005a,b; Yan
soluble EPS from heterotrophic biofilm bacteria significantly et al., 2001). Oh et al. (2007) investigation showed that param-
increased the bactericidal efficiency for most of the photocata- eters of Pt colloid prepared by using the polyol process
lysts. EPS is found to play an important role in controlling the although the adjustment of pH behaves as a key factor in con-
bactericidal reaction kinetics through competition for ROS trolling the nanodimension of the Pt particles, a severe reduc-
with biofilmbacteria. The degradation of cellular substances tion in the metal loading is observed with increasing solution
takes a much longer time to achieve compared with cell inac- pH. According to the zeta potential study, this is attributed
tivation, although the oxidation of carbohydrate and protein to the electrostatic stabilization between Pt particles and car-
followed similar trend as the bacterial killing. The results of bon supports. The zeta potential of the carbon support de-
observations suggest that not all types of organism can repre- creased to negative values with increasing solution pH while
sent the mixture of bacteria in a natural environment, e.g., bio- that of the Pt particles remained constant at a negative charge
film. These findings suggest that nitrogen-doped TiO2 has after pH 6. Therefore, poor adsorption or repulsive forces be-
potential applications in the development of alternative disin- tween the metal colloids and the supports occurs, resulting in
fectants for environmental and medical usage. reduced Pt particle loading. Pt loading and particle size are
also affected by the gas environment during Pt/C synthesis in
3.3. Bio diesel production the polyol process. It is observed that carrying out the entire
process of Pt/C formation in N2 showed very good control
With the increase of environment protection consciousness over Pt particle size whereas the Pt loading is significantly
and decrease of petroleum reserves, biodiesel, defined as the low. When the process of Pt/C formation is carried out in
monoalkyl esters of fatty acids, has been the focus of a consid- the presence of O2, the Pt loading is increased up to
erable amount of recent research as an alternative renewable 36 wt.%. However, the particle size of Pt increases due to
fuel. More and more biodiesel is being used in many countries agglomeration at low solution pH. As a modification to the
such as Germany, France, Italy, USA, Japan and so on polyol process, the reduction of Pt metal ions at elevated tem-
(Bozbas, 2008; Sharma and Singh, 2002). The general method perature with N2 purging followed by the further reduction at
for the preparation of biodiesel is trans esterification reaction room temperature with air showed the best results with almost
of oil and alcohol with homogeneous catalyst (Dias et al., 40 wt.% loading and a small particle size of 2.8 nm.
2008; Helwani et al., 2009). However, the homogeneous cata-
lyst has many shortcomings, such as the difficulty in product 3.5. In drug delivery
isolation, requirement of large quantity of water and environ-
mental pollution by the liquid wastes (Martinez et al., 2004; Carbon nanomaterials are of great interest in applications for
Sharma et al., 2008; Meher et al., 2006). A new trend in the biological fields (Kelly et al., 2008; Yushin et al., 2006). Typi-
preparation of biodiesel is to use ‘‘green’’ method based on het- cally, carbon nanotubes (CNTs) have a feature of endohedral
erogeneous catalyst (Martyanov and Sayari, 2008; Granados filling of 2–10 nm in diameter leading to encapsulation of small
et al., 2007). Despite the solid phase catalytic methods being molecules. CNTs can be heterogeneously surface-functional-
intensively studied, the industrial applications are limited. This ized and stained cytochemically with nonquenching and
fact suggests that further research is necessary to solve current non-photobleaching. Accordingly, CNTs may be suitable for
problems (Gryglewicz, 1999; Liu et al., 2008). Heterogeneous bio-applications in biorecognition and drug delivery systems
catalytic methods are usually mass transfer resistant, time con- (Hayashi et al., 2007; Jang and Yoon, 2003; Peckys et al.,
suming and inefficient (Kouzu et al., 2008). Nanocatalysts have 2002). However the biocompatibility of CNTs is still contro-
high specific surface and high catalysis activities, may solve the versial and the tedious functionalization process of CNT sur-
above problems. They have become the focus of recent research face remains a major obstacle to practical applications
(Shu et al., 2007; Bournay et al., 2005). Wen et al. (2010) studied (Magrez et al., 2006; Cheng et al., 2009). Oh et al. (2010) re-
that the solid base nanocatalyst KF/CaO can be used for bio- ported the fabrication of carbonized polypyrrole nanoparticles
diesel production with yield of more than 96%. The catalyst (CPyNs) with controlled diameters and their textural proper-
is well used to convert the oil with higher acid value into biodie- ties and investigated the potential capability of CPyNs as
sel. It is porous with particle sizes of 30–100 nm. XRD analysis imaging probes and drug carriers based on their porosity, mag-
showed the catalyst has new crystal KCaF3, which increases netic property and biocompatibility. The guest molecule load-
catalytic activity and stability. The high specific surface area ing of CPyNs was conducted with pyrene as a typical
and large pore size are favorable for contact between catalyst hydrophobic dye and the guest molecule-releasing test was per-
and substrates, which effectively improved efficiency of transe- formed with ibuprofen as a typical hydrophobic drug. Poly
sterification. Production of biodiesel from Chinese tallow seed Pyrrole nanoparticles with controlled diameters were prepared
oil has positive impact on the utilization of agricultural and by micelle templating in oil/water emulsions, and CPyNs with
forestry products. three different sizes (55, 76, and 99 nm) were successfully ob-
tained by carbonization of the polymer pre-cursors. CPyNs
3.4. Fuel cell application showed highly microporous compared to zeolite, resulting in
loading guest molecules into CPyNs using phase separation.
There is tremendous interest in the preparation of carbon sup- In addition, the magnetic property of CPyNs provided the
ported electro-catalysts for fuel cell applications (Ahmadi selective separation and targeting. CPyNs sustained in vitro
et al., 1996; Tang et al., 2005; Kim and Popov, 2004; Hirano drug release properties. Importantly, smaller size and amine
et al., 1997). It is well known that the performance of catalysts surface modification of CPyNs provide an improved sustained
property. Due to their superiorities such as microporous struc- 2006; Prado and Leonardo, 2009). In order to avoid this diffi-
ture, monodispersity, magnetism, and biocompatibility, it is cult recuperation, Ivanov et al. (2003) synthesized the TiO2
believed that the CPyNs open the way to use in fields such nanotubes characterized and applied them to the photodegra-
as biomaterials science, including bioimaging and magnetic in- dation of malachite green dye. Recycling studies were followed
duced drug carriers. and compared to traditional TiO2 anatase photocatalyst in or-
der to demonstrate the advantages of nanostructured TiO2 in
3.6. Photocatalytic activity photocatalysis. TiO2 nanotubes presented a photocatalytic
activity lower than TiO2 anatase to degrade malachite green
3.6.1. Photocatalytic decoloration of malachite green dye dye. The catalysts presented their best activity at pH 4. The
High amount of unconsumed dyes produced by textile and great advantage of TiO2 nanotubes is its easy recovery in com-
printing industries are discharged into the waters every day. parison with traditional TiO2 catalyst. Consequently, the nano-
The presence of dyes and pigments in water causes consider- tubes can be recycled and reapplied in many photodegradation
able damage to the aquatic environment (Robinson et al., cycles, maintaining 80% of their activity after 10 cycles of reac-
2001; Pearce et al., 2003; Talarposhti et al., 2001). These con- tion. The pre-cursor TiO2 catalyst lost its activity on the second
taminants result in high chemical oxygen demand (COD), high catalytic cycle.
biochemical oxygen demand (BOD), toxicity, bad smell, and
mainly, are responsible for the coloration of wastewaters 3.6.2. Photodegradation of methylene blue
(Santos et al., 2007; Prado et al., 2004; Chiou and Li, 2002). Soni et al. studied the photocatalytic activity in the visible part
Even at very low concentrations, the color of this kind of con- of the solar spectrum (442 nm) for demonstrated highly orga-
taminants can be recognized, because the presence of dyes in nized mesoporous nanocrystalline titania thin films doped with
water is highly visible. This effect is undesirable because the thiourea. This property, which is of interest for the further
color blocks the sunlight access to aquatic flora and fauna, development of photovoltaic devices operating in sunlight, is
and it reduces the photosynthetic action within the ecosystem revealed by monitoring the photodegradation of methylene
(Srivastava et al., 2004; Cheng et al., 2008). Among many dyes blue upon contact with an N-doped TiO2film as a function
that are applied in manufacture products, malachite green of irradiation time and film thickness (Soni et al., 2008).
must be highlighted. This dye has been used as a food coloring Yuo and Wang, prepared TiO2 sol for the degradation of
additive, as a dye for silk, jute, leather, wool, cotton and paper methylene blue (MB) solution under ultraviolet (UV) irradia-
(Culp and Beland, 1996; Chen et al., 2007). Moreover, this tion. The absorption spectra of MB indicated that the maxi-
compound has also been used as a medical disinfectant, mum wavelength, 663 nm, was almost kept the same. The
antihelminthic, as well as, in aquaculture as a fungicide and performance of 92.3% for color removal was reached after
antiseptic (Rahman et al., 2005; Bekc et al., 2008). The appli- 160 min. The particle size of TiO2 sol was about 22.5 nm. X-
cation of malachite green in aquaculture dates back 1933, due ray diffraction showed that TiO2 consisted of a single anatase
to its high effect against protozoal and fungal infections phase. The small size and anatase phase probably resulted in
(Perez-Estrada et al., 2008; Lee et al., 2001). However, the high photocatalytic activity of TiO2 sol. The degradation ratio
use of malachite green has been contested due to the effects decreased as the initial concentration of MB increased. The
on the reproductive and immune systems and its potential photodegradation efficiency decreased in the order of pH
genotoxic and carcinogenic effects. Many processes have been 2 > pH 9 > pH 7. Regarding catalyst load, the degradation
extensively applied in the treatment of dye-containing waste increased with the mass of catalyst up to an amount of
water such as: incineration, biological treatment, ozonation, 1.5 g L1 then decreased as the mass continued to increase.
and adsorption on solid phases (Garcia-Montano et al., 2008; The addition of H2O2 to TiO2 sol resulted in an increase in
Chu and Ma; 2000; Prado et al., 2003, 2005). However, these the degradation ratio (Yao and Wang, 2010).
procedures have some limitations. The incineration can pro- Choi et al. (2006) describes the application of novel chem-
duce toxic volatiles; biological treatment demands long periods istry methods for the fabrication of robust nanostructured tita-
of treatment and bad smell; ozonation presents a short half-life, nium oxide (TiO2) photocatalysts. Such materials can be
ozone stability is affected by the presence of salts, pH, and tem- applied in the development of efficient photocatalytic systems
perature and the adsorption results in phase transference of for the treatment of water. Mesoporous photocatalytic TiO2
contaminant, not degrading the contaminant and producing films and membranes were synthesized via a simple synthesis
sludge (Garcia-Montano et al., 2008; Chu and Ma; 2000; Prado method that involves dip-coating of appropriate substrates
et al.,2003, 2005). In this way, the heterogeneous photocatalysis into an organic/inorganic sol composed of isopropanol, acetic
becomes an elegant alternative for dye degradation. This acid, titanium tetraisopropoxide, and polyoxyethylenesorbitan
technique presents many advantages over conventional tech- monooleate surfactant (Tween 80) followed by calcination of
nologies such as the dye degradation into innocuous final the coating at 500 C. Controlled hydrolysis and condensation
products (Torres et al., 2006; Prado et al., 2008). Many photo- reactions were achieved through in-taking of water molecules
catalysts have been used to degrade organic pollutants such as released from the esterification reaction of acetic acid with iso-
ZnO, Nb2O5 and TiO2. Among these catalysts, TiO2 is high- propanol. The subsequent stable incorporation of Ti–O–Ti
lighted because of its high catalytic efficiency, high chemical network onto self-assembled surfactants resulted in TiO2 phot-
stability, low cost and toxicity. On the other hand, TiO2 suspen- ocatalysts with enhanced structural and catalytic properties.
sion in water presents a hydrocolloid with a high stability, The properties included high surface area (147 m2/g) and
which makes difficult the separation of this catalyst from water. porosity (46%), narrow pore size distribution ranging from 2
Consequently, the recuperation and re-application of this cata- to 8 nm, homogeneity without cracks and pinholes, active ana-
lyst in other photodegradation reactions becomes hard and tase crystal phase, and small crystallite size (9 nm). These TiO2
with a low efficiency (Prado et al., 2005, 2008; Torres et al., photocatalysts were highly efficient for the destruction of
methylene blue and creatinine in water. High water permeabil- after calcination had the highest photocatalytic activity among
ity and sharp polyethylene glycol retention of the prepared all three catalysts tested, with 95% of AO7 decolorized in 1 h
photocatalytic TiO2/Al2O3 composite membranes evidenced under UV illumination. The doped TiO2 also exhibited sub-
the good structural properties of TiO2 films. In addition, the stantial photocatalytic activity under direct sunlight irradia-
multi-coating procedure made it possible to effectively control tion; with 70% of the dye color removed in 1 h and complete
the physical properties of TiO2 layer such as the coating thick- decolorization within 3 h. Degussa P25 did not cause detectable
ness, amount of TiO2, photocatalytic activity, water perme- dye decolorization under identical experimental conditions
ability and organic retention. using solar light. The decrease of total organic carbon (TOC)
and evolution of inorganic sulfate SO24 ions in dye solutions
3.6.3. Photo catalytic degradation of Azo dyes were measured to monitor the dye mineralization process.
Liu et al. (2005a,b) examined the photocatalytic degradation of
three azo dyes, acid orange 7 (AO7), procion red MX-5B 3.6.4. Photo catalysis
(MX-5B) and reactive black 5 (RB5) using a new type of nitro- TiO2 is regarded as the most efficient and environmentally be-
gen-doped TiO2 nanocrystals. These newly developed doped nign photocatalyst and has been most widely used for photo-
titania nanocatalysts demonstrated high reactivity under visible degradation of various pollutants (Fujishima and Honda,
light (k > 390 nm), allowing more efficient usage of solar light. 1972; Fujishima et al., 2000; Grätzel, 2001; Hay and Raval;
Experiments were conducted to compare the photocatalytic 1998). TiO2 photocatalysts can also be used to kill bacteria,
activities of nitrogen-doped TiO2 nanocatalysts and commer- as has been carried out with E. coli suspensions (Kikuchi
cially available Degussa P25 powder using both UV illumina- et al., 1997). The strong oxidizing power of illuminated TiO2
tion and solar light; result shown that nitrogen-doped TiO2 can be used to kill tumor cells in cancer treatment (Sakai
Figure 1 Different forms of TiO2.

Figure 2 Schematic diagram of photocatalytic process initiated by photon acting on the semiconductor.
et al., 1995). The photocatalytic reaction mechanisms are can be adsorbed on the very large surface, but also for two
widely studied (Fujishima and Honda, 1972; Fujishima et al., additional reasons: (a) they allow the semiconductor small par-
2000; Grätzel, 2001; Hay and Raval; 1998; Beydoun et al., ticles to become almost totally depleted upon immersion in the
1999). The principle of semiconductor photocatalytic reaction electrolyte (allowing for large photovoltages), and (b) the
is straightforward. Upon absorption of photons with energy proximity of the electrolyte to all particles makes screening
larger than the band gap of TiO2, electrons are excited from of injected electrons, and thus their transport, possible (Cahen
the valence band to the conduction band, creating electron– et al., 2000). Ordered mesoporous TiO2 nanocrystalline films
hole pairs. These charge carriers migrate to the surface and re- showed enhanced solar conversion efficiency by about 50%
act with the chemicals adsorbed on the surface to decompose compared to traditional films of the same thickness made from
these chemicals. This photodecomposition process usually in- randomly oriented anatase nanocrystals (Zukalova et al.,
volves one or more radicals or intermediate species such as 2005). Higher efficiencies of solar cells were achieved with

OH, O2, H2O2, and O2, which play important roles in the TiO2 nanotube-based electrodes due to the increase in electron
photocatalytic reaction mechanisms. The photocatalytic activ- density in nanotube electrodes compared to P25 electrodes
ity of a semiconductor is largely controlled by: (i) the light (Ohsaki et al., 2005). Nanoporous electrodes in a core–
absorption properties, e.g., light absorption spectrum and shell configuration, usually a TiO2 core coated with Al2O3
coefficient, (ii) reduction and oxidation rates on the surface (Fabregat-Santiago et al., 2004), MgO (Kumara et al., 2004),
by the electron and hole, and (iii) the electron–hole recombina- SiO2 (Palomares et al., 2003), ZrO2 (Chen et al., 2001), or
tion rate. Large surface area with constant surface density of Nb2O5 (Chen et al., 2001), could improve the performance of
adsorbents leads to faster surface photocatalytic reaction rates. dye-sensitized solar cells. Doped TiO2 nanomaterials also show
In this sense, the larger the specific surface area, the higher the a good promise in the application of DSSCs. For the best
photocatalytic activity is. On the other hand, the surface is a N-doped TiO2 electrodes, the photoinduced current due to vis-
defective site, therefore the larger the surface area, the faster ible light and at moderate bias increased around 200 times
the recombination. Soni et al studied the photocatalytic activ- compared to the behavior of pure TiO2 electrodes (Lindgren
ity in the visible part of the solar spectrum (442 nm) for dem- et al., 2003) (Figs. 1–5).
onstration of highly organized mesoporous nanocrystalline
titania thin films doped with thiourea. High temperature treat-
ment usually improves the crystallinity of TiO2 nanomaterials,
which in return can induce the aggregation of small nanopar-
ticles and decrease of the surface area. Judging from the above
general conclusions, the relation between the physical proper-
ties and the photocatalytic activities is complicated. Optimal
conditions are sought by taking these considerations into ac-
count and may vary from case to case (Beydoun et al., 1999).
3.6.5. Photovoltic
Photovoltaics based on TiO2 nanocrystalline electrodes have
been widely studied on the so-called dye-sensitized nanocrys-
talline solar cell (DSSC) (Irie et al., 2003; Chen et al.,
2005a,b). The structure and properties of the TiO2 electrodes
play an important role in the performance of the DSSC. The
mesoporosity and nanocrystallinity of the semiconductor are Figure 3 Preparation of TiO2 and 10.0 mol% Bi/TiO2 nanome-
important not only because of the large amount of dye that ter particles by solvothermal method.
Figure 4 Concept chart of the nano-composite of Al2O3 and ZrO2ÆTiO2.
preparation of a nanostructural to get a high surface area that

is directly related with catalytic activity (Hwu et al., 1997).
Moreover, photocatalysis of nanocrystalline TiO2 has many
of advantages on wastewater treatment, such as high catalysis
efficiency, energy-saving, non-pollution and can degrade all
kinds of organic pollutants from water effectively. All of these
merits make photocatalysis of TiO2 a fine and attractive meth-
od in the research of water treatment and it is supposed to be
used widely in future. The prepared nano TiO2 catalyst is uni-
form and spherical particles with an average nanoparticles size
of 11.50 nm. In order to evaluate photoactivity of prepared
nano TiO2 catalyst, the photocatalytic degradation of phenol
in a batch reactor was studied. Results reveled that the photo-
activity of the prepared nano TiO2 catalyst and commercial-
ized TiO2 powder (Degussa P25). The figure obviously
indicates that the phenol concentration decreases with the in-
crease of reaction time. The degradation of phenol using pre-
Figure 5 Classical scheme for the production of highly oxidative pared nano TiO2 is higher than the Degussa P25. It is well
species by TiO2 under light irradiation with wavelengths known that the higher efficiency of prepared nano TiO2 is
<400 nm. influenced by many factors such as particle size and surface
area. In this study, the findings show that the prepared nano
TiO2 has larger surface area, higher porosity and is of smaller
3.6.6. Photo catalytic degradation of phenol particle size than the Degussa P25. This is the reason why the
Nanoparticle catalysts are highly active since most of the par- prepared nano TiO2 is more active than the commercialized
ticle surfaces can be available to catalysis. Many of the nano- TiO2 powder for photocatalytic degradation of phenol
catalysts have found applications in ammonia synthesis, (Table 1).
environmental protection, photocatalysis, waste removal, fiber
and mechanical industries. Mohamed et al. (2007) studied the
use of nanocatalyst for photocatalytic degradation of phenol.
Phenol and substituted phenols are widely distributed at low Table 1 Sample labels and treatment condition.
concentration in natural waters, including algal secretion, Sample Treatment condition plasma Chemical
hydrolyzable tannins and flavonoids and humification pro- electrolytic oxidation treatment
cesses, and at high concentrations in some industrial wastewa- pa
nPEO –
ter discharge and agricultural activities (Sobczynski et al., pb
PEO –
2004). Treating phenolic wastewater to harmless level is an pa p
CT-nPEO
arduous process for many biological and chemical processes pb p
CT-PEO
due to its high solubility and stability in water. Although a p
‘‘ ’’: With treatment; ‘‘–’’: without treatment.
wide range of catalyst has been tested, titania (TiO2) seems a
The oxidized coating formed in an electrolyte without addition
to be the most widely used catalyst because of its photocata- of HA.
lytic, conservative nature, low cost, low toxicity, corrosion b
The oxidized coating formed in an electrolyte with addition of
resistant (Moonsiri et al., 2004) and high stability to light HA.
illumination. A way to increase photocatalytic activity is the
3.7. In solid rocket propellants on thermal decomposition of ammonium perchlorate (AP)

which is main oxidizer of composite solid rocket propellant
The use of aluminum particles of sub-micrometer size in the (CSPs). Investigation results showed that in presence of nano
combustion of composite solid propellants has gained recent sized catalyst thermal decomposition of AP enhanced many
attention. Several facets of this application have been reported, fold. Due to small size of catalyst and their large surface area
such as production (Lee et al., 2003; Mench et al., 1998), ther- extent of adsorption increased which enhanced the percentage
mal decomposition (Kwok et al., 2002; Kwon et al., 2004; of thermal decomposition of AP. Burning rate of CSPs also en-
Johnson et al., 2008) in combination with ammonium perchlo- hanced in presence of these nano catalysts as compared to their
rate (AP) (Liu et al., 2004; Kwok et al., 2007), surface coating macro size.
of aluminum particles (Bocanegra et al., 2007; Trunov et al.,
2005), ignition (Trunov et al., 2006) and oxidation or combus- 3.8. TiO2 in energy application
tion of aluminum particles (Kwon et al., 2003; Huang et al.,
2007) including bimodal blends of micrometer and sub- Titanium dioxide (TiO2) is a biocompatible and environmen-
micrometer sized particles (Romonadova and Pokhil, 1970), tally benign and has been widely used as a pigment (Salvador
combustion of pressed pellets of aluminum and AP with addi- et al., 2000; Zallen and Moret, 2006; Braun et al., 1992; Reck
tives (Dokhan et al., 2002), aluminized composite propellants and Richards, 1999). Recent enormous research efforts dedi-
(De Luca et al., 2005; Galfetti et al., 2006, 2007; Jayaraman cated to TiO2 materials have been most fascinated with the dis-
et al., 2009), and collection of aluminum agglomerates formed covery of the phenomenon of photocatalytic splitting of water
during the combustion of aluminized propellants (Galfetti on a TiO2 electrode by the researchers (Fujishima and Honda,
et al., 2007). Jayaraman et al. (2009) studied nano-aluminum 1972; Fujishima et al., 2000; Tryk et al., 2000). An exponential
particles of 50 nm size are added to composite solid propel- growth of research activities has been seen in nanoscience and
lants based on ammonium perchlorate and hydroxyl-termi- nanotechnology in the past decades (Burda et al., 2005; Chen
nated poly-butadiene binder that exhibit plateau burning rate et al., 2005a,b; Chen and Mao, 2006, 2007; Cozzoli et al.,
trends and those including burning rate catalysts. The 2006; Millis and Hunte, 1997; Grätzel, 2000, 2001). TiO2
nano-aluminized propellant burning rates are compared with nanomaterials, including nanoparticles, nanorods, nanowires,
corresponding micro-aluminized and non-aluminized ones in and nanotubes, are widely investigated for various applications
the 1–12 MPa pressure range. The mid-pressure extinction of in photocatalysis, photovoltaics, batteries, photonic crystals,
the matrixes containing the fine-sized ammonium perchlorate sensors, ultraviolet blockers, smart surface coatings, pigment,
particles in the propellant along with the binder is investigated and paints (Salvador et al., 2000; Zallen and Moret, 2006;
in all the cases to understand the mechanism of plateau-burn- Braun et al., 1992; Reck and Richards; 1999; Fujishima and
ing. The non-aluminized propellants show plateau burning Honda, 1972; Fujishima et al., 2000; Tryk et al., 2000; Burda
wherein the mid-pressure extinction occurs in the correspond- et al., 2005; Chen et al., 2005a,b; Chen and Mao, 2006,
ing matrixes. Plateau burning regime occurs in the micro- 2007; Cozzoli et al., 2006; Millis and Hunte, 1997; Grätzel,
aluminized propellants too, but not always at the same 2000, 2001; Lan et al., 2005; Holland et al., 1998, 1999; Mor
pressures as the corresponding non-aluminized propellants. et al., 2003; Hwang et al., 2003; Meilert et al., 2005; Pfaff
Replacement of micro-aluminum by nano-aluminum increases and Reynders, 1999; Hagfeldt and Grätzel; 1995; Linsebigler
the propellant burning rate by 100% regardless of the other et al., 1995). Various methods, such as sol–gel, sol, hydrother-
parameters considered in this paper. These burning rates al- mal/solvothermal, physical/chemical vapor deposition, electro-
ways show low pressure-exponents in the elevated pressure deposition, etc., have been successfully used in making TiO2
range. On the other hand, the plateau burning rate trends ob- nanomaterials. In the nanometer scale, new physical and
served in the non-aluminized and micro-aluminized formula- chemical properties emerge and they vary with the sizes and
tions are washed out in the corresponding nano-aluminized shapes of the nanomaterials. The movement of electrons and
formulations. These results show that the nano-aluminized holes in semiconductor nanomaterials is governed by the
propellant burning rate is controlled by the near-surface igni- well-known quantum confinement, the transport properties re-
tion and diffusion-limited combustion of nano-aluminum lated to phonons and photons are largely affected by the size
agglomerated to 5 lm in size, at elevated pressures. The in- and geometry of the materials, and the specific surface area
crease in plasticizer content in the propellants leads to shift and surface-to-volume ratio increase dramatically as the size
in the plateau burning regime to lower pressures. The increase of a material decreases (Burda et al., 2005; Chen et al.,
in nano-aluminum size decreases the burning rate but the 2005a,b; Chen and Mao, 2006, 2007; Cozzoli et al., 2006;
opposite effect is observed with micro-aluminum. The burning Millis and Hunte, 1997). The high surface area brought about
rate monotonically increases with nano-aluminum content in by small particle size is beneficial to most TiO2-based devices,
bimodal aluminized propellants. Addition of micron-sized cat- as it facilitates reaction/interaction between the devices and
alysts does not contribute to burning rate enhancement in interacting media, which mainly occurs on the surface and de-
nano-aluminized propellants, although they increase the burn- pends on the surface area. As the size, shape, and crystal struc-
ing rate by 100% in non-aluminized and micro-aluminized ture of TiO2 nanomaterials change, not only does surface
propellants, as expected. Nano-sized catalysts increase the stability vary, but the transitions between different phases of
burning rate by 5% in nano-aluminized propellants, how- TiO2 under pressure or heat become size dependent as well.
ever. Agglomeration is observed in self-quenched matrixes
with nano-aluminum to the extent of 1–5 lm, but this could 3.9. Photochemical activity of TiO2
still be too small to offer two phase flow losses in rockets.
Singh et al. (2008, 2009a,b,c) studied catalytic properties of Matsunaga et al. (1985) reported the novel concept of
several compounds like mono oxide, ferrites, metal alloys etc. photochemical sterilization. Microbial cells were killed
photoelectrochemically with semiconductor powder (plati- junction solar cell. Porous CdS and porous TiO2 films were
num-loaded titanium oxide, TiO2/Pt). Coenzyme A, (CoA) in deposited on plastic substrates by a self assembly method. Typ-
the whole cells was photo-electrochemically oxidized and, as ical pore sizes were 80 and 70 nm, respectively. These can be
a result, the respiration of cells was inhibited. Inhibition of used in nano-structured solar cell configuration where the pores
respiratory activity caused death of the cells. Lactobacillus aci- are filled with a p-type absorber material. Due to the nano-
dophilus, Saccharomyces cerevisiae and E. coli (103 cells/ml, structured character of the absorber, the transport path for
respectively) were completely sterilized when they were incu- the light generated electrons in the absorber is reduced. At
bated with TiO2/Pt particles under metal halide lamp irradia- the same time, the optical path for photon absorption is in-
tion for 60–120 min. creased due to multiple reflections.
Another study of Matsunaga et al. (1988) reported a novel
photochemical sterilization system in which E. coli cells were 3.11. Waste water treatment
sterilized with photosemiconductor powders (titanium oxide).
For sterilization that could be used in practice, it was neces- Halogenated organic compounds (HOCs) are among the most
sary to separate the TiO2 powders from the cell suspension. widely distributed water pollutants in industrialized countries.
Therefore, semiconductor powders were immobilized on acet- These organic molecules play an important role as solvents
ylcellulose membranes. We constructed a continuous-steriliza- and additives in different industries such as the pharmaceutical
tion system consisting of a TiO2-immobilized acetylcellulose production or in the IT branch. HOCs are mostly hazardous
membrane reactor, a mercury lamp, and a masterflex pump. and toxic compounds which have very often a high persistence
As a result, under the various sterilization conditions exam- and may cause serious health problems such as cancer or
ined, E. coli (10(2) cells per ml) were sterilized to less than mutagenic damage. Therefore, a complete destruction of these
1% survival when the cell suspension flowed in this system compounds is aspired or even mandatory. Ordinary wastewa-
at a mean residence time of 16.0 min under irradiation ter treatment works cannot handle the problem. Thus, high
(1800 microeinsteins/m2 per s). We found that this system priced and energy-intensive methods still have to be employed
was reusable. to solve this problem. Common practice to dispose of indus-
trial wastewaters contaminated with threshold load of organic
3.10. Thin film solar cell solvents and only traces of HOCs is incineration. However, or-
ganic compounds such as alcohols could be removed by bacte-
Many nano-structured materials are now being investigated rial treatment in a wastewater treatment plant. The critical
for their potential applications in photovoltaic, electro-optical, component leading to cost-intensive disposal is frequently
micromechanical and sensor devices (Whitesides and the HOC. Current detoxification techniques such as adsorp-
Grzybowski, 2002; Duan et al., 2003; McAlpine et al., 2003). tion on activated carbon or oxidation of the wastewater com-
Advantage of the benefits is also to make inexpensive and effi- ponents do not lead to an environmentally friendly and
cient solar cells on a large scale. To this end, nanostructured economically priced solution. For example huge amounts of
layers in thin film solar cells offer three important advantages. activated carbon would be necessary in order to remove
First, due to multiple reflections, the effective optical path for HOC traces from water loaded with other sorption-active com-
absorption is much larger than the actual film thickness. Sec- ponents. In the case of oxidation, excess amounts of oxidant
ond, light generated electrons and holes need to travel over a are required because all reduced water components would be
much shorter path and thus recombination losses are greatly oxidized. The risk derives when insufficient amounts of oxi-
reduced. As a result, the absorber layer thickness in nano- dant are applied, that even more toxic components can occur
structured solar cells can be as thin as 150 nm instead of sev- if the oxidation is not complete. The last and often practiced
eral micrometers in the traditional thin film solar cells (Ernst consequence is an excess-priced incineration. However, the
et al., 2003). Third, the energy band gap of various layers incineration of aqueous waste is a waste of energy. Therefore,
can be tailored to the desired design value by varying the size for a medium-sized enterprise a decentralized selective dehalo-
of nano-particles. This allows for more design flexibility in the genation treatment of wastewater can give a significant eco-
absorber and window layers in the solar cell. In particular nomic advantage. Hildebrand et al. (2008) suggested an idea
nano-structured CdS, CdTe and TiO2 are of interest as win- to detoxify the water by a selective destruction of the HOCs
dow and absorber layers in thin film solar cells (Singh et al., using the method of HDH on palladium-containing nano-
1995, 2004; Singh and McClure, 2003; Linam et al., 2001; catalysts. Detoxification means that persistent HOCs are con-
Calixto et al., 2000; Mathew et al., 2000). Singh et al. verted into organic compounds which can easily be removed
(2004a,b) used the self-assembly process to fabricate a variety by biodegradation in a wastewater treatment plant. Reductive
of nano-structured films including CdTe and CdS on ITO- hydrodehalogenation reactions are very efficient and selective.
coated glass substrates. In addition nano-porous CdS and That means, only the toxic and harmful halogenated com-
TiO2 films were fabricated on a plastic substrate with a view pounds are affected by the catalytic reaction following the pre-
to making devices on a lightweight, flexible substrate. The re- sented reaction type.
sults indicated a blue shift in the absorption with an effective
Pd-Catalyst
band gap of 2.8 eV: This opens the possibility of using nano- RX þ H2 ! RH þ HX
crystalline n-type CdTe as a window layer in an n-CdTe/p-CdTe
homo junction solar cell. Nano-crystalline CdS films on ITO- For this reaction H2 or a hydrogen source as reducing agents
coated glass substrates exhibited particle sizes of 15 nm and are required. The products are predominantly non-toxic
an effective band gap of 2.98 eV as compared to the 2.4 eV va- organic molecules and small amounts of HX. There are, how-
lue for the band gap of bulk CdS. This makes nano-crystalline ever, some exceptions such as benzene formed by dechlorina-
CdS a better window material in an n-CdS/p-CdTe hetero tion of chlorobenzene. Palladium containing catalysts in the
form of catalyst pellets are commonly used in fixed bed arrangements due to minimized mass-transfer limitations.
reactors in technical processes such as hydrogenation. For Magnetite particles are suitable catalyst carriers because of
environmental applications such as ex-situ groundwater their high resistance against milieu parameters. Their magne-
treatment, Pd catalysts have been tested already (Lowry and tism allows a complete extraction of the nanoparticles from
Reinhard, 2000; Mc-Nab et al., 2000). Kopinke et al. (2003) the treated water by magneto-separation.
defined the specific catalytic activity APd as measure of the Water treatment using TiO2 semiconductor as a durable
Pd efficiency. Extremely active catalysts for cyclic batch or heterogeneous photocatalyst has been the focus of environ-
continuous flow-through reactor applications can be produced mentalists in recent years. Liu et al. (2006a,b) developed an
on the basis of ferromagnetic nano-sized carrier colloids (mag- inexpensive and highly efficient approach for synthesizing
netite, Fe3O4) containing only traces of Pd (0.1 wt.%). Nano- nitrogen-doped TiO2 with lower band-gap energy that can re-
sized Pd catalysts have been successfully tested for selective spond to visible light. Doping on the molecular scale led to an
hydrodehalogenation of wastewater pollutants at the labora- enhanced nitrogen concentration of up to 21.8%. Reflectance
tory scale. Dehalogenation using Pd on nano-scale supports measurements showed the synthesized N-doped TiO2 nanopar-
shows the true inherent activity of Pd clusters which is several ticles are catalytically active with the absorbance that extends
orders of magnitude higher than reached in fixed-bed arrange- into the visible region up to 600 nm. The water purification po-
ments due to minimized mass-transfer limitations. Magnetite tential of this new class of compound was evaluated by study-
particles are suitable catalyst carriers because of their rather ing the photodegradation of Acid Orange 7 (AO7) and E. coli.
high resistance against milieu parameters. Their magnetism al- Experiments were conducted to compare the photocatalytic
lows the extraction of the nano-particles from the treated activities of N-doped TiO2 nanocatalysts and commercially
water by means of magneto-separation which makes a reuse available Degussa P25 power under identical solar light expo-
of the catalyst possible. Alternative H-donor such as formic sure. N-doped TiO2 demonstrated superior photocatalytic
acid was successfully tested. Beside the study of the opportu- activities in both chemical compound degradation and bacteri-
nities and the high potentials of such catalyst systems, the cidal reactions. The result of this study shows the potential of
evaluation of their potential environmental risks is in applying new generations of catalyst for wastewater purifica-
progress. tion and disinfection.
Mackenzie et al. (2007) showed two different examples for
ex situ and in situ water treatment using nano-sized materials. 3.12. In environment protection
Two novel colloidal particles have been developed and tested
in initial studies for (i) the in situ generation of sorption/reac- Sulfate radical-based advanced oxidation technologies (SR-
tion barriers based upon zero-valent iron on sorption-active AOTs) are attracting considerable attention due to the high
carbon carriers (carbo-iron) for application in subsurface oxidizing ability of SRs to degrade organic pollutants in aque-
water treatment and (ii) the selective catalytic elimination of ous environments. Yang et al. (2009) studied current concerns
halogenated hydrocarbons using Pd on magnetic carriers as and challenges in SR-AOTs, including (i) need of heteroge-
agent for ex-situ waste water treatment. The common ground neous activation of sulfate salts using transition metal oxides,
for both applications is the utilization of nano-particles for (ii) nanoscaling of the metal oxide catalysts for high catalytic
dehalogenation reactions in the aqueous phase in order to min- activity and promising properties with respect to leaching,
imize mass transport limitation and therefore permit high and (iii) easy removal and recovery of the catalytic materials
decontamination rates. These water treatment applications after their applications for water and wastewater treatments.
have been selected for presentation in order to show the wide In this study a novel approach of using Fe-Co mixed oxide
applicability of nano-sized materials in environmental technol- nanocatalysts for the heterogeneous activation of peroxy-
ogy. With carbo-iron (20 wt.% Zero-Valent Iron {ZVL}), a mono-sulfate (PMS) to generate SRs targeting the decomposi-
novel material is provided which forms stable colloidal solution of 2,4-dichlorophenol was introduced. Ferromagnetic Co-
tions up to high concentrations and Ca2+ concentrations. Sta- Fe2O4 composites formed by thermal oxidation of a mixed
bilizers such as polyanionic substances can help to keep the phase of Fe and Co exhibited significant implications for the
particles mobile under aquifer conditions. Humic acid as a nat- efficient and environmentally friendly activation of PMS,
ural product can act as stabilizer; however, carboxymethyl cel- including (i) the cobalt species in CoFe2O4 are of Co(II), unlike
lulose is able to stabilize much higher particle concentrations Co3O4 showing some detrimental effects of Co(III) on the
of carbo-iron and facilitates long transport distances. Carbo- PMS activation, (ii) CoFe2O4 possesses suppressed Co leach-
iron has proved its dehalogenation activity for chlorinated ing properties due to strong Fe-Co interactions (i.e., Fe-Co
and brominated C1- and C2-hydrocarbons in aqueous solu- linkages), and (iii) Fe-Co catalysts in form of CoFe2O4 are eas-
tion. Furthermore, the hydrophobic nature of carbo-iron per- ier to recover due to the unique ferromagnetic nature of Co-
mits its distribution in NAPL phases where dehalogenation Fe2O4. In addition, the presence of Fe was found to be
can be performed without the application of additives. This beneficial for enriching hydroxyl group content on the Fe-Co
is a great advantage over pure nano-sized ZVI, which requires catalyst surface, which is believed to facilitate the formation
additives for source treatment. Extremely active catalysts for of Co(II)-OH complexes that are vital for heterogeneous
cyclic batch applications can be produced on the basis of fer- PMS activation.
romagnetic nano-sized carrier colloids containing only traces
of Pd (0.1 wt.%). Nano-sized Pd catalysts have been success- 3.13. In fuel
fully tested for waste water problems at the laboratory scale.
Dehalogenation using pure Pd colloids or Pd on colloidal sup- Gas to liquids (GTL) process is considered as an alternative
ports shows the true inherent activity of Pd clusters which is process to produce liquid fuels from natural gas due to high
several orders of magnitude higher than reached in fixed-bed oil price. GTL process consists of synthesis gas production,
Fischer–Tropsch synthesis, and product work-up. In GTL 3.14. Alcohol oxidation

process, the capital cost of synthesis gas production is about
60% of total capital cost (Rostrup-Nielsen, 1993; Ross et al., Methanol and ethanol are the most studied alcohols for Direct
1996; Aasberg-Petersen et al., 2001; Yagi et al., 2005; Peña Alcohol Fuel Cell (DAFC) application (Wasmus and Kuwer,
et al., 1996; Armor, 1999; Tsang et al., 1995). It is very impor- 1999; Vigier et al., 2004a,b; Batista et al., 2004; Xia et al.,
tant to adjust a H2/CO ratio for Fischer–Tropsch synthesis. 1997; Lamy et al., 2004). Use of ethanol as fuel in DAFCs pro-
In practical syngas production, representative reforming pro- vides many advantages over methanol due to its re-newability,
cesses such as steam reforming of methane (SRM), carbon low toxicity, safety, high energy density, and its easy produc-
dioxide reforming of methane (CRM) have some drawbacks tion in great quantities from biomass (Delime et al., 1999;
because both reforming reactions require the additional pro- Coutanceau et al., 2008; Wang et al., 1995). The main prob-
cess to adjust H2/CO ratio (Beurden, 2004; Roh et al., lems of DAFCs are poor performance of electrocatalysts, espe-
2002, 2004; Chin et al., 2006; Wang et al., 1996). Partial oxi- cially anode catalysts at lower temperatures and the severe fuel
dation of methane (POM) can be considered as an alternative crossover from anode to cathode, which leads to poisoning of
due to the suitable H2/CO ratio for Fischer–Tropsch synthe- cathode catalyst (Arico et al., 2005; Baglio et al., 2007; Lamy
sis. However, it is difficult to control the POM process due to et al., 2001). The activity improvement of anode catalysts is
the hot spot and explosion danger (Ashcroft et al., 1991; Roh helpful to reduce fuel permeation through electrolyte. Pt has
et al., 2001a,b; Koh et al., 2007; Song and Guo, 2006). On been demonstrated as the only active and stable noble metal
the contrary, combined steam and carbon dioxide reforming for alcohol oxidation, particularly in acid medium. However,
of methane (CSCRM) is a feasible process for the direct con- it is well known that pure platinum is readily poisoned by
trol of the H2/CO ratio by adjusting the feed ratio of steam CO-like intermediates of methanol or ethanol electro-oxida-
and carbon dioxide. Thus, CSCRM is an adequate reforming tion (Lamy et al., 2000). On the other hand, the high cost of
process to produce syngas for Fischer–Tropsch synthesis (Qin the platinum limits its use. One of the grand challenges in
et al., 1996; Jing et al., 2004; Bhattacharyya et al., 1998; DMFC development is to reduce the usage of Pt precious me-
Zhang et al., 2004; Choudhary and Mondal, 2006; Jeong tal. One approach to cost reduction is to use the Pt-based al-
et al., 2006). In general, it is necessary to develop economical loys to reduce the Pt loading. Another effective approach is
catalysts with high activity and stability for CSCRM. Ni cat- to increase the utilization efficiency of Pt electrocatalysts by
alysts have commercially been applied for SRM because they exploring the high surface area supports such as high surface
are economical compared to noble metal based catalysts area carbon. Methanol or ethanol oxidation on Pt is only pos-
(Sehested, 2006; Pompeo et al., 2005). However, supported sible at potentials where adsorbed CO and other poisoning
Ni catalysts have some problems such as Ni particle sintering intermediates are effectively oxidized, leading to a significant
and coke deposition, resulting in catalyst deactivation (Oh overpotential and hence loss in efficiency. Kadirgan et al.
et al., 2003). To prevent coke formation in SMR, excess steam (2009) investigated the effect of Pt–Pd/C nano-sized electrocat-
is usually employed, which results in H2 enriched syngas (Hou alysts on oxidation of alcohols. The experiments confirm that
et al., 2006; Roh et al., 2007). However, excess steam cannot Pt–Pd/C nano-particles synthesized lead to synergistic effect
be used in CSCRM to adjust a H2/CO ratio for Fischer– toward methanol and ethanol oxidation, particularly impor-
Tropsch synthesis. Therefore, it is necessary to develop cata- tant than that of commercial Pt/C ETEK. Pt–Pd binary cata-
lysts with high coke resistance for CSCRM. It has been re- lyst was more active toward oxidation of methanol than
ported that Ni catalyst supported on nano-particles of ZrO2 ethanol because not only strongly adsorbed intermediate
could be highly active and stable for CRM (Sehested; 2006). (e.g., CO) but also other oxidation reaction intermediates, such
It is also reported that nano-sized Ni–Ce–ZrO2 catalyst could as acetaldehyde and acetic acid may be adsorbed after
be active and stable in CRM (Roh et al., 2004). Therefore, it dissociative chemisorptions of ethanol molecule during elec-
is inferred that the crystallite size of Ni and support plays an tro-oxidation process. Although an enhancement of the reac-
important role in catalytic activity as well as stability in meth- tion kinetic for both alcohols was observed increasing the
ane reforming reactions under severe conditions. Very re- working temperature, apparent activation energy values were
cently, Liu et al. (2006a,b) reported that Ni/MgO–Al2O3 smaller for methanol oxidation than ethanol oxidation reac-
catalyst exhibited the highest activity as well as stability tion on Pt–Pd/C electrode indicating easier oxidation kinetic
among supported Ni catalysts. While Kee et al. (2008) inves- for methanol.
tigated the effect of Ni crystallite size and SMSI on the coke Recently, there is a growing concern about the damage
resistance to suppress coke deposition. Pre-calcination tem- done to the natural environment due to the human activity.
perature of the support plays a significant role in determining Industry is usually blamed for the introduction of pollutants
the crystallite size of both Ni and support and metal to sup- to the environment. However, the changes in agriculture bring
port interaction. With increasing the pre-calcination tempera- about similar problems. For example, application of fertilizers
ture, Ni crystallite size increases and BET surface area and pesticides leads to the pollution of soil and ground water.
decreases due to the collapse of support. In general, large Some of them are resistant to environmental degradation and
Ni particles have a weak interaction with support, while have the tendency to accumulate in the food chain. Therefore,
highly dispersed Ni particles have a SMSI, resulting in high there is an interest in development of innovative, efficient,
resistance to coke deposition. As a result, the Ni/MgO– cheap and environment friendly techniques for the degradation
Al2O3 catalyst pre-calcined at 800 C exhibits the highest coke of these pollutants. Among such poorly exhausting pesticides,
resistance due to the smallest Ni crystallite size and SMSI, organophosphorus insecticides have been most heavily con-
resulting in the highest catalytic activity and stability. Thus, sumed in agriculture and horticulture. Hence, a lot of re-
the Ni/MgO–Al2O3 catalyst will be a promising catalyst in searches have been engaged in the mineralization technology
CSCRM for the GTL process. of organophosphorus insecticides. For example, the method
of high power ultrasonic irradiation is usually used to treat ture. Some of the nanoparticles are used like Silver
some dyestuff wastewaters owing to its advantages, such as nanoparticles (Ag-np) are being used increasingly in wound
cleanness, high efficiency and non-secondary pollution dressings, catheters, and various household products due to
(Tezcanli-Guyer and Ince, 2003; Ge and Qu, 2003; Ince their antimicrobial activity. The toxicity of starch-coated silver
et al., 2001). As known to all, under the function of ultrasonic nanoparticles was studied by AshaRani et al. (2009) using nor-
irradiation, the dissolved vapors and gases in the liquid be- mal human lung fibroblast cells (IMR-90) and human glioblas-
come cavitations bubbles and then entrap the organic pollu- toma cells (U251). The toxicity was evaluated using changes in
tants, which attain very high temperatures that the organic cell morphology, cell viability, metabolic activity, and oxida-
pollutants are directly decomposed or indirectly oxidized by tive stress. Ag-np reduced ATP content of the cell caused dam-
formed hydroxyl (ÆOH) radicals during momentary collapse age to mitochondria and increased production of reactive
of cavitations bubbles (Suslick et al., 1990; Okitsu et al., oxygen species (ROS) in a dose-dependent manner. DNA
2005; Sivakumar and Pandit, 2001; Ṕetrier and Suslick, damage, as measured by single cell gel electrophoresis (SCGE)
2000). However, the degradation of organic pollutants by high and cytokinesis blocked micronucleus assay (CBMN), was also
power ultrasound usually needs lots of energy, costly treated dose-dependent and more prominent in the cancer cells. The
equipment and long reaction time (Taghizadeh and Mehrdad, nanoparticle treatment caused cell cycle arrest in G2/M phase
2003). Previously, in order to overcome these drawbacks of possibly due to repair of damaged DNA. Annexin-V propidi-
mere ultrasonic irradiation, the anatase titanium dioxide um iodide (PI) staining showed no massive apoptosis or necro-
(TiO2) powders were used as the sonocatalysts combined with sis. The transmission electron microscopic (TEM) analysis
low power ultrasonic irradiation to treat methyl parathion indicated the presence of Ag-np inside the mitochondria and
solution (Wang et al., 2006). Because of the slightly narrow en- nucleus, implicating their direct involvement in the mitochon-
ergy gap and appropriate adsorbability, the rutile TiO2 powder drial toxicity and DNA damage. A possible mechanism of
was used after heat treatment as sonocatalyst in this work and toxicity is proposed which involves disruption of the mito-
satisfying results were obtained. The influences of reaction chondrial respiratory chain by Ag-np leading to production
parameters were established on sonocatalytic degradation of of ROS and interruption of ATP synthesis, which in turn cause
methyl parathion. In addition, both micron-sized and nano- DNA damage. It is anticipated that DNA damage is aug-
sized rutile TiO2 powders were used to compare their catalytic mented by deposition, followed by interactions of Ag-np to
activities. The results indicated that the degradation of methyl the DNA leading to cell cycle arrest in the G2/M phase. The
parathion sonocatalytically progressed more rapidly in the higher sensitivity of U251 cells and their arrest in G2/M phase
presence of micron-sized rutile TiO2 powder than in the pres- could be explored further for evaluating the potential use of
ence of nano-sized rutile TiO2 powder, which is different from Ag-np in cancer therapy.
the case, where micron-sized and nano-sized anatase TiO2 At present, nanofilaments are not exclusively based on car-
powders were used. In the degradation, the TiO2 powder was bon atoms but can be produced from many inorganic materi-
used as sonocatalyst because of its unique photochemical, pho- als in the form of nanotubes and nanowires. It is essential to
tostable, inexpensive and non-toxic characters (Karcher et al., systematically assess the acute toxicity of these newly synthe-
1999; Poulios et al. 1998). Here, the ultrasonic irradiation in- sized materials since it cannot be predicted from the known
stead of ultraviolet light was used to degrade the methyl para- toxicity of the same material in another form. Magrez et al.
thion in aqueous solution in the presence of micron-sized and (2009) studied the cellular toxicity of TiO2-based nanofila-
nano-sized rutile TiO2 powders. In conclusion, the method of ments in relation to their morphology and surface chemistry.
sonocatalytic degradation for organic pollutants is expected These structures produced by hydrothermal treatment were
to be promising as an inexpensive and environment-friendly titanate nanotubes and nanowires with a NaxTiO2+d composi-
technology of wastewater purification with huge industrializa- tion. The cytotoxic effect was mainly evaluated by MTT assays
tion prospect on the basis of further research works. Wang et combined with direct cell counting and cytopathological anal-
al. (2007) experimental result showed that the sonocatalytic yses of the lung tumor cells. This work clearly demonstrated
performance of micron-sized TiO2 powder is obviously better that the presence of NaxTiO2+d nanofilaments had a strong
than that of nano-sized rutile TiO2 powder. The research re- dose-dependent effect on cell proliferation and cell death.
sults demonstrated the feasibilities of sonocatalytic degrada- Nanofilament internalization and alterations in cell morphol-
tion of methyl parathion and other organic pollutants in ogy were observed. Acid treatment performed to substitute
wastewater. Especially, this method is applicable to the non- Na+ with H+ in the NaxTiO2+d nanofilaments strongly en-
and low-transparent wastewater. The degradation of methyl hanced the cytotoxic action. This effect was attributed to struc-
parathion depends on the amount of rutile TiO2 catalysts, ini- tural imperfections, which are left by the atom diffusion during
tial concentration of methyl parathion solution, acidities, tem- the substitution. On the basis of these findings, it is concluding
perature and ultrasonic frequency and intensity. The optimal that TiO2-based nanofilaments are cytotoxic and thus precau-
conditions for obtaining high degradation percentage of tions should be taken during their manipulation.
methyl parathion are considered to be initial methyl parathion Given the emergence of nanotherapeutics and nanodiag-
concentration of 50 mg L1, micron-sized rutile TiO2 catalyst nostics as key tools in today’s medicine, it has become of crit-
amount of 1000 mg L1, and ultrasonic frequency of 40 kHz, ical importance to define precisely the interactions of
output power of 50 W, pH 10.0 and at 20 C for about 80 min. nanomaterials with biological systems and to characterize the
resulting cellular response. Hutter et al. (2010) reported the
3.15. Nanotoxicology interactions of microglia and neurons with gold nanoparticles
(GNPs) of three morphologies, spheres, rods, and urchins,
Several works are reported in the literature in field of nanotox- coated with poly(ethylene glycol) (PEG) or cetyl trimethylam-
icology which will be one of the major applications in near fu- monium bromide (CTAB). Microglias are the resident immune
cells of the brain, primarily involved in surveillance, macro- gins to release at a high rate until efficiency of 100% is
phagy, and production of cytokines and trophic factors. Anal- achieved. The rate of reaction depends crucially on initial tem-
ysis by dark-field microscopy and by two-photon-induced perature of water. Hence, the mass of water was reduced to
luminescence (TPL) indicates that the exposure of neural cells employ released energy to increase water temperature and,
to GNPs resulted in (i) GNP internalization by both microglial consequently, to increase hydrogen production rate. The opti-
cells and primary hippocampal neurons, as revealed by dark- mum value of salt-to-aluminum mole ratio for achieving high
field microscopy and by two-photon-induced luminescence activation, air-storage capability and 100% efficiency was ob-
(TPL), (ii) transient toll-like receptor 2 (TLR-2) up-regulation tained to be 2. When immersed in water, at initial temperatures
in the olfactory bulb, after intranasal administration in trans- of 55 and 70 C, the powder lead to average hydrogen genera-
genic mice, in vivo, in real time, and (iii) differential up-regulation rate of 101 and 210 ml/min per 1 g of Al, respectively.
tion in vitro of TLR-2 together with interleukin 1 alpha (IL- To increase the rate of corrosion, three different alloys/com-
1a), granulocyte macrophage colony-stimulating factor (GM- posites of aluminum were prepared by mechanical alloying
CSF) and nitric oxide (NO) in microglia. The study demon- and activated with optimum salt-to-aluminum mole ratio.
strates that GNP morphology and surface chemistry strongly The alloys/composites formed galvanic cells after being im-
influence the microglial activation status and suggests that mersed in water. In the case of aluminum–bismuth alloy, the
interactions between GNPs and microglia can be differentially average hydrogen generation rate increased to 287 and
regulated by tuning GNP nanogeometry. 713 ml/min per 1 g of Al, respectively.
3.16. Production of hydrogen for fuel cell

4. Conclusion
The cleanliness of hydrogen and the efficiency of fuel cells ta-
ken together offer an appealing alternative to fossil fuels. The field of nanocatalysis (the use of nanoparticles to catalyze
Implementing hydrogen-powered fuel cells on a significant reactions) has undergone an explosive growth during the past
scale, however, requires major advances in hydrogen produc- decade, both in homogeneous and heterogeneous catalysis.
tion, storage, and use. Splitting water renewably offers the Nanoparticles have a large surface-to-volume ratio compared
most plentiful and climate-friendly source of hydrogen and to bulk materials, they are attractive to use as catalysts. Cata-
can be achieved through electrolytic, photochemical, or bio- lysts daily accelerate and boost thousands of different chemical
logical means. Whereas presently available hydride com- reactions, and thereby form the basis for the multibillion dollar
pounds cannot easily satisfy the competing requirements for chemical industry worldwide and indispensable environmental
on-board storage of hydrogen for transportation, nanoscience protective technologies. Research in nanotechnology and
offers promising new approaches to this challenge. Fuel cells nanoscience is expected to have a great impact on the develop-
offer potentially efficient production of electricity for transpor- ment of new catalysts. The detailed understanding of chemistry
tation and grid distribution, if cost and performance challenges of nanostructures and the ability to control materials on the
of components can be overcome. Hydrogen offers a variety of nanometer scale will ensure a rational and cost efficient devel-
routes for achieving a transition to a mix of renewable fuels. opment of new and more capable catalysts for a chemical
Aluminum, one of most reactive metals, rapidly corrodes in process.
strong acidic or alkaline solutions but passivates at pH of
about 5–9. Czech and Troczynski (2010) has determined that
the passivation of aluminum in this range of pH, and in partic-
Acknowledgments
ular in regular tap water, can be substantially prevented after
milling of aluminum with water-soluble inorganic salts (re-
The authors are grateful to Chemistry Department of KSKV
ferred to as ‘‘WIS’’), such as KCl or NaCl. Ensuing corrosion
University, Bhuj for laboratory facility. One of the authors
of Al in tap water, with accompanying release of hydrogen and
Shalini Chaturvedi is also thankful to CSIR for Research asso-
precipitation of aluminum hydroxide, at normal pressure and
ciate (RA) fellowship.
moderate temperatures (55 C) is rapid and substantial.
For example, 92% of the Al in the Al–WIS system when
milled for 1 h and 81% when milled for 15 min, corrodes References
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Journal of Saudi Chemical Society (2012) 16, 307–325

King Saud University

Journal of Saudi Chemical Society

Applications of nano-catalyst in new era

Received 27 September 2010; accepted 30 January 2011

Figure 1 Different forms of TiO2.

Figure 4 Concept chart of the nano-composite of Al2O3 and ZrO2ÆTiO2.

preparation of a nanostructural to get a high surface area that

3.7. In solid rocket propellants on thermal decomposition of ammonium perchlorate (AP)

Fischer–Tropsch synthesis, and product work-up. In GTL 3.14. Alcohol oxidation

3.16. Production of hydrogen for fuel cell

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