RESEARCH

Durairajan et al.
Experimental investigation and control the toxic emissions in IC engines by nano materials,
Discovery Sci., 2012, 1(1), 3-9, www.discovery.org.in
www.discovery.org.in/ds.htm 2012 discovery publication. All rights reserved
3
Durairajan A
1,*
, Kavitha T
2
, Rajendran A
2
1.Department of Mechanical Engineering, K.S.R. College of Engineering, Tiruchengode-637215, Namakkal (DT), Tamil Nadu, India, E-mail:
durairajan.rohan@gmail.com
2.Department of Physics, Nehru Memorial College, Puthanampatti, Trichy, Tamil Nadu, India, E-mail: kavithaphysics@gmail.com
3.Department of Physics, Nehru Memorial College, Puthanampatti, Trichy, Tamil Nadu, India, E-mail: rajendran20@gmail.com
*Corresponding author: Durairajan A, Department of Mechanical Engineering, K.S.R. College of Engineering, Tiruchengode-637215,
Namakkal (DT), Tamil Nadu, India, E-mail: durairajan.rohan@gmail.com, Tel: (+91) 8015655878.
Received 17 April; accepted 19 May; published online 25 June; printed 29 June 2012
ABSTRACT
Automobile plays an important role in contribution to the pollution. Air pollution is predominately emitted through the exhaust of
motor vehicles and the combustion of fossil fuels. Pollution control is playing a vital role to control the future generation and toxic
emissions like CO, NOX and HC. The objective of the work is to reduce the emissions from the automobiles through design and
manufacturing of nano catalytic converter by replacing the existing expensive metals such as Platinum. Nano Materials like nano
Rhodium and nano Palladium were obtained by using chemical vapour deposition (CVD) technique. The obtained nano powder
was deposited in the honey comb structure. By using the nano catalytic converter the pollution is reduced.
Key words: Nano catalytic converter; Nano palladium; Nano rhodium; Nano materials; Automobile pollution; CVD.
Abbreviations: CVD - Chemical vapour deposition; NM - Nano Meter; HC - Hydrocarbon; NOx - Nitrogen-di-oxide; CO -
Carbon- monoxide; SI - Spark ignition; CI - Compression ignition.
1. INTRODUCTION
Nanotechnology is a science of controlling
individual atoms and molecules. One of the
serious problems facing the world is the drastic
increase in environmental pollution by internal
combustion engines. All transport vehicles; both
SI (Spark ignition) and CI (Compression ignition)
are equally responsible for emitting different kind
of pollutants (Rajadurai and Tagomori, 2000). Two
stroke SI engines have certain advantages such
as compactness, lightweight, simple construction
and low cost and low nitric oxide emissions; they
suffer from problems of high specific fuel
consumption, high hydrocarbon and high carbon
monoxide emissions. Some of the primary kinds
having direct hazardous effects such as carbon
mono oxide, hydrocarbons, nitrogen oxides, etc.
other, the secondary pollutants, which undergo a
series of reactions in the atmosphere and become
hazardous to health (Joseph et al., 2001). The
emissions exhausted into the surroundings pollute
the atmosphere and cause global warming, acid
rain, smog, odors, and respiratory and other
health hazards. A pollutant is a phenomenon
which changes the balance of the environment
and nature under normal condition. Carbon-di-
oxide is not considered as pollutant, as nature
recycles. If carbon-di-oxide exceeds 5000ppm,
then it becomes a health hazard. Using nano
catalytic converter, pollution is controlled by
means of catalytic reaction (Ketteler et al.,
2002).
2. MATERIALS AND METHODS
2.1. Synthesis
In general, synthesis of nanoparticles refers to a
combination of two or more entities that together
form something new; alternately, it refers to the
creating of something by artificial means (Table
1 and Table 2).
1. Laser ablation
2. Arc discharge
3. Plasma enhanced CVD
4. Chemical vapor deposition (CVD)
Here we used CVD method (Fig.1 and Fig.2) to
synthesis the Nano palladium & Nano rhodium
1. Easy method
2. Gas phase deposition
3. Large scale possible
RESEARCH Discovery Science, Volume 1, Number 1, July 2012
Science
Experimental investigation and control the toxic
emissions in IC engines by nano materials
Chemical Vapour
Deposition (CVD):
The execution of
chemical reactions to
form a more complex
molecule from
chemical precursors.
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2
7
8

5
4
8
5
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I
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S
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2
7
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7
7
RESEARCH
Durairajan et al.
Experimental investigation and control the toxic emissions in IC engines by nano materials,
Discovery Sci., 2012, 1(1), 3-9, www.discovery.org.in
www.discovery.org.in/ds.htm 2012 discovery publication. All rights reserved
4
4. Relatively cheap
Here the oven is maintained at 720
0
c, palladium is
kept above the quartz boat as a sample. The C2H2
and N2 is passed through the quartz tube.
2.2. Automobile Pollution
It is defined as the introduction of chemicals,
particulate matter, or biological materials to the
atmosphere that cause harm or discomfort to the
living organisms. Due to the advancement in
science and technology there is a drastic
improvement in automobile production which
results in more amount of harmful gas is let into
the atmosphere. These gases react with the
atmosphere and pollute it.
2.3. Catalytic converter
A catalytic converter is a device used to reduce
the toxicity of emissions from an internal
combustion engine. A catalytic converter converts
the harmful toxic combustion products and its
byproducts into less-toxic substances (Fig.3).
Catalysis is the process in which the rate of a
chemical reaction is increased by means of a
chemical substance known as a catalyst. Unlike
other reagents a catalyst is not consumed during
the chemical reaction (Apostolescu et al., 2006).
Thus, the catalyst may participate in multiple
chemical transformations, although in practice
catalysts are secondary processes. There are
millions of cars on the road that are potential
sources of air pollution. In a major effort to reduce
vehicle emissions, car makers have developed
an interesting device called a catalytic converter,
which treats the exhaust before it leaves the car
and removes a lot of the pollution (Hizbullah et
al., 2004).
It is the most effective after treatment
process for reducing engine emission.
Catalytic converter is generally called as
three way catalytic converter because it
promotes in reduction of HC, CO and NOx.
It consists of steel container of honeycomb
structure inside which contains porous
ceramic structure through which the gas
flows.
It consists of small embedded partials of
catalytic materials that promote oxidation
reaction in exhaust gas.
Catalytic converter uses alumina as base
material because it can withstand high
temperature.
2.4. Catalytic Materials
Many types of material often used as catalyst in
the recent years. Proton acids are probably the
Table 1 Physical method for preparation of nanoparticles
Method Advantages Limitations
Evaporation condensation
method
High purity powder The limitation of mass production
Plasma heating method
High melting point and low vapour pressure materials
(W, Al2O3, SiO2, C)
Very expensive equipment
CO2 laser method Low vapor pressure materials
Difficult for the application of Metal nano
powder
Mechanical alloy method Nano powder of metal alloy Agglomeration & introduction of impurity
Pulsed wire evaporation wire Metal wire source
Low energy consumption & Friendly
environment
Table 2 Chemical method for preparation of nanoparticles
Method Advantages Limitations
Chemical Vapor Deposition (CVD)
Mass production facility Impurity contamination & the danger of chemical materials
Liquid phase reduction method
Hydro-thermal synthesis
Sol-gel method
Table 3 Nanoparticles-Categories and
Applications
Nanostructure
Example Material or
Application
Nanotubes Carbon, (fullerenes)
Nanowires
Metals, semiconductors,
oxides
Nanocrystals,
quantum dots
Insulators, semiconductors,
metals
Figure 1
Schematic representation of CVD
Figure 3
Over view of catalytic converter
Figure 2
Chemical vapor deposition set up
RESEARCH
Durairajan et al.
Experimental investigation and control the toxic emissions in IC engines by nano materials,
Discovery Sci., 2012, 1(1), 3-9, www.discovery.org.in
www.discovery.org.in/ds.htm 2012 discovery publication. All rights reserved
5
most widely used catalysts, especially for the
many reactions involving water, including
hydrolyses and its reverse. Multifunctional solids
often are catalytically active, e.g. zeolites,
alumina, certain forms of graphitic carbon etc.
Transition metals such as platinum, palladium,
rhodium, iron, silver are often used to catalyses
redox Reactions (Table 3 and Table 4), (Jacob
Klimstra and Nederlandse Gasunie, 1989).
2.5. General principles of catalysis
Catalysts generally react with one or more
reactants to form intermediate substances that
subsequently give the final reaction product, in the
process regenerating the catalyst. The following is
a typical reaction, where C represents the catalyst,
X and Y
are reactants, and Z is the product of the reaction
of X and Y:
X + C XC (1)
Y + XC XYC (2)
XYC CZ (3)
CZ C + Z (4)
Although the catalyst is consumed by reaction 1, it
is subsequently produced by reaction 4, thus the
overall reaction is listed below:
X + Y Z
As a catalyst is regenerated in a reaction, often
only small amounts are needed to increase the
rate of the reaction. In practice, however, catalysts
are sometimes consumed in secondary
processes.
2.6. Catalysis and reaction
Catalyst is used serves for two purposes,
1. Enhances the reaction rate
2. Direct the reactants to specified product
General potential energy diagram showing the
effect of a catalyst in the chemical reaction of X
+ Y to give Z. Due to presence of the catalyst
reaction occurs in different pathway which
results in lower activation energy. The final
result and the overall thermodynamics are the
same. Potential energy diagram is shown in
Fig.4. Rate of reaction(R) is inversely
proportional to exponential of the activation
energy. Let k be the reaction rate constant, Ca,
Cb be the concentration at point of time of
reactant molecules and x, y be the reaction
order. Thus rate of reaction is represented as
Rate of reaction R =kCaxCby
Catalysts work by providing an (alternative)
mechanism involving a different transition state
and lower activation energy. The effect is due to
the molecular collisions have the energy needed
to reach the transition state. Catalysts do not
change the favorableness of a reaction: they
have no effect on the chemical equilibrium of a
reaction because the rate of both the forward
and the reverse reaction are both affected.
2.7. Mechanism of catalytic reaction
Mechanism of catalyst was carried by
chemisorptions which is the type of adsorption
where the molecules adhere to the surface of
catalyst through the formation of chemical bond.
Strength of the adsorption in the order of,
O2>C2H2>CO>H2>CO>N2. Variation of
chemisorptions among metals is represented as
follows, Au>Cu>Pd>Pt>Rh>Co>Ni>Ag>Mn>Fe>
Mo>W>Nb>Ta>Ti Based on this it is clearly
represented that Au can readily react with metal
and can act as efficient catalyst for most of the
reaction (Fig.5). At the same time Ti has low
chemisorptions thus it cannot be used as
catalyst.
Table 4 Pollutants and its characteristics
Pollutant Characteristics
Nitrogen oxides It is an reddish-brown toxic gas emitted from high temperature combustion
Carbon monoxide Colourless, odorless, non-irritating but very poisonous gas.
Particulate matter
These are tiny particles of solid or liquid suspended in a gas which cause health hazards such as heart disease,
altered lung function
Sulfur oxides Generally SO2 reacts with atmosphere to form H2SO4, and thus acid rain
Figure 4
Diagram of Potential Energy
Figure 5
Model of catalytic reaction
Chemisorption:
Chemisorption is a sub-
class of adsorption,
driven by a chemical
reaction occurring at
the exposed surface. A
new chemical species
is generated at the
adsorbant surface (e.g.
corrosion, metallic
oxidation).
RESEARCH
Durairajan et al.
Experimental investigation and control the toxic emissions in IC engines by nano materials,
Discovery Sci., 2012, 1(1), 3-9, www.discovery.org.in
www.discovery.org.in/ds.htm 2012 discovery publication. All rights reserved
6
2.8. Steps for Dispersion of
Particles on to the Catalytic Converter
1. Capillary Impregnation - It is the process by
which adsorption of nano particles on to the
surface of catalyst converter when the
particles are dispersed in the liquid medium.
The adsorption of particles on to catalytic
converter takes place unto saturation limit.
Further drying and calcinations at high
temperature results in fixing of particles on to
catalytic converter.
2. Drying - Drying process take place at 110oc
for the matter of one hour in the closed
furnace.
3. Calcinations - Calcinations process take
place at 550oc for the matter of five hour in
the closed furnace. Thus results in fixing of
particles on to the catalytic converter.
2.9. Types of Catalyst
Generally catalyst can be classified into two types
Homogeneous catalyst
Heterogeneous catalyst
Electro catalyst
Homogeneous Catalyst - Homogeneous
catalysts are those in which reactant and product
are of same phase. One example of
homogeneous catalysis involves the influence of
H+ on the etherification of esters, e.g. methyl
acetate from acetic acid and methanol.
Heterogeneous Catalyst - Heterogeneous
catalysts are those in which reactants and product
are of different phase. For example, in the Haber
process, finely divided iron serves as a catalyst for
the synthesis of ammonia from nitrogen and
hydrogen.
Electro Catalyst - In the context of
electrochemistry, specifically in fuel cell
engineering, various metal-containing catalysts
are used to enhance the rates of the half
reactions that comprise the fuel cell. One
common type of fuel cell electro catalyst is
based upon nanoparticles of platinum that are
supported on slightly larger carbon particles
when this platinum electro catalyst is in contact
with one of the electrodes in a fuel cell.
2.10. Types of Catalytic Converter
The types of converter are listed below
Monolithic Converter
Two way converter
Three way converter
Dual bed converter
Three-Way Catalytic Converter - Three-way
catalytic converter is widely used in the
automobile industries. The three-way catalytic
converter is scheduled to perform three
simultaneous tasks, a) nano palladium:
reduction catalyst, b) nano rhodium: oxidation
catalyst, and c) the control system (Fig.6 and
Fig.7).
2.10.1. The Reduction Catalyst
The reduction catalyst is the first stage of the
catalytic converter. It uses Nano palladium to
help reduce the nitrogen oxide emissions. When
such molecules come in contact with the
Figure 6
Three way catalytic converter
Figure 7
Construction of 3 way converter
PROPERTIES OF CATALYST
Surface area and pore size - High surface area results in maximum dispersion of catalytic compound. Smaller pores
size result in increase in catalytic activity.
Particle size distribution - Thus more number of particles dispersed result in increase in catalytic activity. Thus huge
number of particle distribution obviously increases the catalytic action.
Wash coat thickness - Optical microscope study is often used to obtain wash coat thickness directly. The space
between wash coat and monolith gives the wash coat thickness measurement. Thus wash coat formed must be as
small as possible.
Adhesion - Common method for the measure of the adhesion between wash coat monotyth is passing jet of air that
simulates velocity used to measure adhesion between substrate and catalyst. There must be sufficient adhesion
between molecules for higher catalytic activity.
Calcination:
Calcination (calcining)
is a thermal treatment
process in presence of
air applied to ores and
other solid materials to
bring about a thermal
decomposition, phase
transition, or removal of
a volatile fraction. The
calcination process
normally takes place at
temperatures below
the melting point of the
product materials.
RESEARCH
Durairajan et al.
Experimental investigation and control the toxic emissions in IC engines by nano materials,
Discovery Sci., 2012, 1(1), 3-9, www.discovery.org.in
www.discovery.org.in/ds.htm 2012 discovery publication. All rights reserved
7
catalyst, the catalyst rips the nitrogen atom out of
the molecule and holds on to it, freeing the oxygen
in the form of O2. The nitrogen atoms bond with
other nitrogen atoms that are also stuck to the
catalyst, forming N2.
2.10.2. The Oxidization Catalyst
The oxidation catalyst is the second stage of the
catalytic converter. It reduces the unburned
hydrocarbons and carbon monoxide by burning
(oxidizing) them over a nano rhodium catalyst.
This catalyst aids the reaction of the CO and
hydrocarbons with the remaining oxygen in the
exhaust gas.
2.10.3. The Control System
The third stage is a control system that monitors
the exhaust stream, and uses this information to
control the fuel injection system. There is a heated
oxygen sensor (also called a Lambda Sensor)
mounted upstream of the catalytic converter
(Fig.8), meaning it is closer to the engine than the
converter (Stanley L.Genslak, 1972). This sensor
tells the EEC-V PCM how much oxygen is in the
exhaust. The EEC-V can increase or decrease the
amount of oxygen in the exhaust by adjusting the
air-to-fuel ratio. This control scheme allows the
EEC-V to ensure that the engine is running at
close to the stoichiometric point, while also making
sure that there is enough oxygen in the exhaust to
allow the oxidization catalyst to burn the unburned
hydrocarbons and carbon monoxide (Kureti et al.,
2003). The rear most Lambda sensors are not
used to adjust the engine mixture but simply to
identify the performance of the Catalytic
Converters. In ideal conditions they should show a
constant output indicating that the Cats are
working as intended. Ripple which mirrors the
output of the pre-CAT sensors indicates Cats that
are starting to fail.
2.11. How three way Catalytic Converters
Reduce Pollution?
Most modern cars are equipped with three-way
catalytic converters. "Three-way" refers to the
three regulated emissions it helps to reduce -
carbon monoxide, un-burnt hydrocarbons and
nitrogen oxide molecules. The converter uses
two different types of catalysts, a reduction
catalyst and an oxidization catalyst (Steve
Seldlitz, 1974). Both types consist of a ceramic
structure coated with a metal catalyst, we used
nano palladium and nano rhodium. The idea is
to create a structure that exposes the maximum
surface area of the catalyst to the exhaust
stream, while also minimizing the amount of
catalyst required. There are three main types of
structures used in catalytic converters - ceramic
honeycomb, metal plate and ceramic beads
Reduction of nitrogen oxides to nitrogen and
oxygen
2NOx xO2 + N2
Oxidation of carbon monoxide to carbon dioxide
2CO + O2 2CO2
Oxidation of un-burnt hydrocarbons (HC) to
carbon dioxide and water
CxH2x + 2xO2 xCO2 + 2xH2O
2.12. Applications of Catalytic Converter
Petrol engine emission control
Diesel engine emission control
Food processing industries
Chemical manufacturing industries
Gas turbines
3. RESULTS AND DISCUSSIONS
3.1. NOx Reduction
The variations of NOx value with brake power
value and at different conditions are shown in
Fig.9. The NOx value keeps on decreasing on
introduction of catalytic converter and finally
reaches the minimum value on using nano
catalytic converter. Thus at no load condition
there is about 33.33% decrease in NOx value
and at peak load condition there is about 54.3 %
decrease in NOx value. This is due to the fact
that NOx undergoes catalytic reaction with
catalytic particles such as Nano palladium, Nano
rhodium, results in the production nitrogen and
oxygen as the end product. Thus there is steady
decrease in NOx value with the introduction of
the Nano catalytic converter.
3.2. HC Reduction
Figure 8
Lambda sensor
Figure 9
Variation of Nox reduction with brake power
Stoichiometric point:
The stoichiometric
point is a term
commonly used to
describe a particular
fuel/air ratio in a
combustion engine.
RESEARCH
Durairajan et al.
Experimental investigation and control the toxic emissions in IC engines by nano materials,
Discovery Sci., 2012, 1(1), 3-9, www.discovery.org.in
www.discovery.org.in/ds.htm 2012 discovery publication. All rights reserved
8
The variations of HC value with brake power value
and at different conditions are shown in Fig.10.
The HC value keeps on decreasing on
introduction of catalytic converter and finally
reaches the minimum value on using Nano
catalytic converter. Thus at no load condition
there is about 72.1% decrease in HC value and
at peak load condition there is about 68.8 %
decrease in HC value. This is due to the fact that
HC undergoes catalytic reaction with catalytic
particles such as nano palladium, nano rhodium
results in the production water and oxygen as
the end product. Thus there is steady decrease
in HC value with the introduction of the nano
catalytic converter.
3.3. CO Reduction
The variations of CO value with brake power
value and at different conditions are shown in
the Fig.11. The CO value keeps on decreasing
on introduction of catalytic converter and finally
reaches the minimum value on Nano catalytic
converter. At no load condition there is about
60% decrease in CO value and at peak load
condition there is about 40 % decrease in CO
value. This is due to the fact that CO undergoes
catalytic reaction with catalytic particles such as
nano palladium, nano rhodium results in the
production carbon di oxide and oxygen as the
end product. Thus there is steady decrease in
CO value with the introduction of the nano
catalytic converter.
4. CONCLUSION
Nano palladium and nano rhodium particles (90-
100 nm) were synthesized and characterized by
using chemical vapor deposition method. The
nano catalytic converter efficiently decreases the
emission of NOx, HC and CO components.
SUMMARY OF RESEARCH
1. A detailed work has been done on synthesis and characterization of nano palladium and nano rhodium by using chemical
vapor deposition.
2. The particles are found to be in dispersed state with the particle size ranging from 90-100 nm.
3. The engine exhaust test has been carried out.
4. By using the nano catalytic converter 33.33% decrease in NOx value at no load condition and about 54.3 % decrease in
NOx value at peak load condition.
5. Also HC value is decreasing 72.1% at no load condition and 68.8% at peak load condition.
6. At no load condition 60% decrease in CO value and at peak load condition 40% decrease in CO value.
7. Using nano catalytic converter, the pollution level was reduced successfully.
FUTURE ISSUES
1. What other chemical vapor deposition based nanoparticles employing in pollution control?
2. Which method of preparation is efficient to make nano palladium and nano rhodium particles are more potent in pollution
control?
3. Is nano catalytic converter applicable to control pollution according to cost factor?
DISCLOSURE STATEMENT
There is no conflict of interest and financial support for the proposed research work.
ACKNOWLEDGMENTS
We thank the principal, professors and lecturers those who are all given enormous support to our research work. We extend a
special thanks to our friends and technicians in the department of physics.
Figure 10
Variation of HC reduction with brake power
Figure 11
Variation of CO reduction with brake power
RESEARCH
Durairajan et al.
Experimental investigation and control the toxic emissions in IC engines by nano materials,
Discovery Sci., 2012, 1(1), 3-9, www.discovery.org.in
www.discovery.org.in/ds.htm 2012 discovery publication. All rights reserved
9
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Apostolescu et al.
(2006): In-Depth
study of the catalytic
reduction, gives
solution to use of less
expensive materials.
Joseph et al. (2001):
This study gives
description about the
pottasium promotes
iron oxide as catalyst
for catalytic reaction.