Cleaner Vehicle Emissions
the exhaust gas.
1. Introduction
The internal combustion (IC) engine is the most
efficient and reliable power plant in the transporta-
tion (petrol and diesel engines) and heavy machinery
(diesel engine) sector. IC engines are expected to be
around until: (i) fuel shortages become a serious
issue; (ii) new, less-polluting, and more-efficient
technologies are developed as a replacement; or (iii)
emissions regulations, set by environmental agencies
to improve air quality, become unachievable by the
engine and vehicle manufacturers.
Since the 1970s, catalytic emission control technol-
ogies for the automotive industry have been
developed, in parallel with engine and fuel technol-
ogies, initially to control CO, HC, and NOx emissions
from petrol engines. Today, emission regulations
have also been established in diesel engines to re-
duce particulate matter (PM), in addition to the
other three pollutants. Further, emission regula-
tions are periodically updated with new pollutants,
such as the greenhouse gases CH4 and CO2, or
criteria, for example, particulate size and number,
being added.
Concerns over CO2 greenhouse emissions, and
fuel security issues, have seen the rise in the
development of vehicles with much-improved fuel
economy, that is, lightweight vehicles, hybrids,
and vehicles with diesel engines. Nevertheless, in
present applications, catalytic converters have been
adopted as the main approach for pollution control.
Significant progress has been made in developing
these technologies and the catalytic materials
required.
2. Gasoline Engines and Vehicles
2.1 Three-way Catalytic Converter
The first catalysts used for vehicle emissions control
during the 1970s were relatively simple. These
oxidation catalysts were composed of a precious
metal, such as platinum, supported on fine particles
of a catalyst support, for example, high surface area
alumina, which was, in turn, coated onto catalyst
pellets packaged into a metal canister welded into the
exhaust system. These catalysts were introduced to
the USA for the 1975 emissions legislation, which
required the control of hydrocarbons and carbon
monoxide; early NOx standards could be achieved by
engine design alone. To successfully remove both
hydrocarbon and CO from a petrol exhaust using an
oxidation catalyst, a net oxidizing atmosphere was
needed, and, for this purpose, air was injected into
CO oxidation
2COðgÞ þ O2 ðgÞ-2CO2 ðgÞ ð1Þ
Hydrocarbon oxidation
Cn Hm ðgÞ þ ðn þ m=4ÞO2 ðgÞ-nCO2 ðgÞ þ 12mH2 OðgÞ ð2Þ
For example:
C8 H18 ðgÞ þ 1212O2 ðgÞ-8CO2 ðgÞ þ 9H2 OðgÞ ð3Þ
After these early successes, the catalysts were
coated onto monolith supports, such as those shown
in Fig. 1; today, these supports are still used in nearly
all catalytic converter systems.
The next technological advance was to address
NOx emissions. Two catalysts were placed in series,
with the first catalyzing the conversion of NOx into
N2 under net reducing conditions, by exploiting the
presence of gas-phase reductants (especially CO), and
the second acting as an oxidation catalyst to remove
CO and hydrocarbon as before.
NO reduction (CO)
2NOðgÞ þ 2COðgÞ-N2 ðgÞ þ 2CO2 ðgÞ ð4Þ
However, this two-bed system was made redundant
by the early 1980s due to the development of a single
catalyst capable of the simultaneous conversion of all
three pollutants, that is, the three-way catalyst
(TWC). This was made possible due to technological
developments in three areas:
(i) the replacement of carburetors by electronic
fuel injection systems, allowing more precise mixtures
of air/fuel (A/F ratio) to be maintained;
(ii) the measurement of oxygen levels in the
exhaust using oxygen sensors; and
(iii) microprocessor control to feed back informa-
tion from the oxygen sensor (engine running lean/
rich) to the injection system.
With more precise control, and with knowledge of
the oxygen content of the exhaust gas, it is possible to
maintain the A/F mixture at or very close to
stoichiometry—therefore, all three pollutants can be
removed over one catalyst, as shown in Fig. 2. Other
important reactions taking place in a TWC are as
follows:
Water–gas shift (WGS) reaction
COðgÞ þ H2 OðgÞ"CO2 ðgÞ þ H2 ðgÞ ð5Þ
Steam reforming
Cn Hm ðgÞ þ nH2 OðgÞ-nCOðgÞ þ ðn þ m=2ÞH2 ðgÞ ð6Þ
NO reduction (H2)
2NOðgÞ þ 2H2 ðgÞ-N2 ðgÞ þ 2H2 OðgÞ ð7Þ
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Cleaner Vehicle Emissions

Figure 1
Examples of monolith substrates. (Left) Cordierite and (right) stainless steel. Image courtesy of Johnson Matthey.

100

90

80
CO
70
Operating window

HC
Conversion (%)

60 NOx
50

40

30

20

10

0
0.97 0.98 0.99 1 1.01 1.02 1.03 1.04 1.05
Equivalence ratio
Figure 2
CO, HC, and NOx conversions for a TWC with changing A/F equivalence ratio (1 is stoichiometric; approximately
14.7 air to each hydrocarbon molecule).

2.2 TWC composition
The catalyst is coated onto the walls of the monolith
material in the form of a slurry material, known as
washcoat, leading to a thin, porous catalyst layer (30–
150 mm) within the monolith. These monoliths are
often formed from a ceramic material, known as
cordierite (2MgO  2Al2O3  5SiO2), but they can also
be formed from stainless steel; a typical cordierite
monolith has 400 channels in  2 (64 channel openings
cm  2), but can also come with 900 cm  2 or even
1200 cm  2. Cordierite is used as it has a low
coefficient of thermal expansion and can therefore
withstand the high heating rates encountered when

2

the engine first starts—typically, the exhaust gas
temperature can reach several hundred degrees in less
than a minute. Metallic monoliths tend to be used
when the space on the vehicle is limited since the
monolith can be welded directly into the exhaust. The
washcoat containing all the parts of the catalyst is
typically composed of:
(i) catalyst support material, for example, g-Al2O3;
(ii) catalyst stabilizers/promoters, for example,
BaO, La2O3;
(iii) active constituents of the catalyst, typically
platinum and/or palladium, and rhodium; and
(iv) oxygen storage component, ceria (CeO2).
The exact formulation depends on many factors,
such as the vehicle type, the market, legislation, metal
prices, and so on. Platinum group metals (PGMs) are
used because they are very tolerant to poisons, for
example, sulfur, present in vehicle exhausts (com-
pared with base metals); without any external
damage, these catalysts usually operate successfully
for periods beyond the lifetime of the vehicle or for
periods determined by the legislated time/mileage.
The Pt, Pd, and Rh are very expensive. However,
they only make up a tiny fraction of the total
washcoat, for example, 1%.
The addition of ceria to the catalyst is necessary to
improve the conversion of hydrocarbon, CO, and
NOx. This is because, despite the excellent control of
the A/F ratio, fluctuation still occurs, though only
slightly to each side of the stoichiometric point. Ceria
can store oxygen in the exhaust in its lattice under
fuel-lean conditions, promoting the reduction of NOx
to N2, and then use this oxygen to oxidize hydro-
carbons and CO under fuel-rich conditions. In this
way, ceria dampens the variations in the A/F ratio
and improves the catalyst performance over a wider
window of operating conditions:
2CeO2 þ CO-Ce2 O3 þ CO2 ð8Þ
Ce2 O3 þ 12O2 -2CeO2 ð9Þ
Ceria also enhances the WGS activity of Pt–Rh
TWCs, and hence promotes CO removal under fuel-
rich conditions; in addition, it can act as a structural
promoter, stabilizing the precious metals and alumi-
na against sintering and particle growth.
3. Diesel or Lean-burn Engines
Diesel engines have several advantages compared to
petrol engines, that is, high torque, fuel economy (low
CO2), durability, and ability to use a range of fuels.
However, due to their image (noisy, dirty, heavy, and
low performance) in the past they were mainly used
in nonroad and heavy-duty vehicle applications.
Concerns over global warming, and improvements
Cleaner Vehicle Emissions
in design, have lead to a rise in the popularity of
diesel vehicles over the past 10 years or so, especially
in Europe.
In a diesel engine, the required amount of fuel is
injected into an excess of air in the engine cylinder.
The resulting exhaust gas therefore still contains a
large amount of oxygen; thus, TWCs, which rely on a
stoichiometric mixture, cannot be employed for diesel
pollution control. Diesel aftertreatment can be
divided into three loose categories:
(i) catalysts for oxidation, that is, hydrocarbon
and CO removal;
(ii) catalysts and filters for PM removal; and
(iii) catalysts for NOx abatement.
Usually, a combination of catalysts is required for
removal of all the pollutants, for example, putting a
filter in series to remove PM, followed by selective
catalytic reduction (SCR), for NOx control.
3.1 Diesel Oxidation Catalysts
A diesel oxidation catalyst (DOC) is employed to
remove CO and hydrocarbons using the oxygen in
the exhaust (5–15% of the gases). It also oxidizes NO
to NO2, which, if left unchecked, results in elevated
levels of NO2 at the exhaust pipe exit. In practice, this
is controlled by defining the appropriate catalyst
formulation, size, and PGM loading.
Hydrocarbon oxidation, for example
C12 H26 ðgÞ þ 1812O2 ðgÞ-12CO2 ðgÞ þ 13H2 OðgÞ ð10Þ
NO oxidation
2NOðgÞ þ O2 ðgÞ"2NO2 ð11Þ
Furthermore, NOx abatement technology can be
used to address this problem, and, indeed, NO2
formation over a DOC is an essential part of some
diesel aftertreatment systems. DOCs are usually
washcoated onto ceramic monoliths, as is the case
for the TWC. Typical washcoats are made up of the
support material, for example, g-Al2O3, and the
active metal component, which can be Pt and/or Pd.
Under certain conditions, DOCs can also contribute
a small NOx reduction function to their performance
by using the hydrocarbon present; typically, this is
low and only occurs over a narrow temperature
range.
NO reduction (HC)
 m  m
Cn Hm ðgÞ þ 2n þ NOðgÞ- n þ N2 ðgÞ þ nCO2 ðgÞ
2 m4
þ H2 OðgÞ ð12Þ
2
A further function, improving the hydrocarbon
performance, can be added to the DOC by including
zeolites. These adsorb hydrocarbons when the
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Cleaner Vehicle Emissions
catalyst is cold, that is, at ‘‘cold start’’ immediately
after start up. The hydrocarbons are then desorbed
and oxidized as the temperature increases to that
required for catalytic oxidation to occur.
3.2 Diesel PM Control
The most successful and widely used materials for
PM emission control are wall-flow filters, also known
as diesel particulate filters (DPFs). Typically con-
structed from cordierite, silicon carbide (SiC), or
aluminum titanate (Al2TiO5), these devices capture
the PM in their porous wall structure as the gas is
forced through the wall from the inlet channel to
outlet channel (Fig. 3). At their simplest level, the
filters are bare and not coated with a catalyst;
however, multifunctional systems can be devised by
adding a catalyst, for example, DOC, or a NOx
abatement catalyst.
To maintain the long-term operation of the filters,
it is necessary to remove the filtered PM. This can be
done using passive regeneration, which is a continual
process, or periodic active regeneration (or both). In
a passive system, the NO2 in the exhaust is used to
oxidize the PM to CO and (mainly) CO2. To
maximize the NO2 content in the exhaust gas, a
DOC is used upstream to convert NO to NO2; this is
the basis of the very successful Continuously
Regenerating Trap (CRTs) system. Even greater
passive regeneration performance can be achieved by
adding a Pt catalyst to the filter; this is the Catalyzed
CRT (CCRTs) device. However, in some cases,
passive regeneration cannot be used, for example, not
enough NOx available or the temperature being too
low. In this case, active regeneration, using oxygen in
the exhaust, is periodically applied to the system.
However, the temperature required for a useful PM
Figure 3
A schematic showing the operating principle of a wall-
flow filter. Courtesy of Corning Inc. Reproduced from
Twigg M V 2007 Progress and future challenges in
controlling automotive exhaust gas emissions. Appl. Catal.
B: Environ. 70, 2–15, with permission from Elsevier.
4
oxidation rate is 500–5501C, far above that observed
in typical diesel exhausts (200–3001C). Therefore,
extra heat is provided, usually by injecting hydro-
carbon (i.e., fuel) into the exhaust upstream the DOC
to generate an exotherm. With active regeneration, it
is necessary to carefully control the oxidation
temperature since a runaway reaction can lead to
irreversible filter damage. Furthermore, active meth-
ods result in a fuel penalty.
3.3 Diesel NOx Removal Catalyst Technology
Catalytic NOx removal from the diesel exhaust is
usually achieved by either the addition of a separate
reductant, in SCR, or by engine/combustion manage-
ment using a lean NOx trap (LNT).
Urea/ammonia SCR is a process in which NOx is
reduced by ammonia, typically introduced as a urea
solution (Adblue, 32.5% aqueous solution) sprayed
into the exhaust upstream of the catalyst. Typical
catalysts for urea SCR include supported vanadium
oxide (V2O5), and iron or copper supported on
zeolite, which is washcoated onto a monolith (as for
the TWC).
Urea decomposition
NH2 CONH2 -NH3 þ HNCO ð13Þ
Hydrolysis
HNCO þ H2 O-NH3 þ CO2 ð14Þ
NO SCR
4NH3 þ 4NO þ O2 -4N2 þ 6H2 O ð15Þ
NO2 SCR
8NH3 þ 6NO2 -7N2 þ 12H2 O ð16Þ
Fast SCR
2NH3 þ NO þ NO2 -2N2 þ 3H2 O ð17Þ
The reaction of ammonia and NOx occurs at
around 200–4501C; however, for low temperature
applications, some flexibility can be achieved by
system design. For example, by providing an
optimized NO/NO2 feed of 1/1 to the catalyst, the
reaction rate is significantly enhanced. At high
temperatures, care must be taken that the NH3 is
not oxidized itself. The urea injection rate is of key
importance in urea SCR; too much would result in
ammonia emitted to the atmosphere and, to ensure
this does not happen, an ammonia slip catalyst
(ASC), usually Pt based, can be fitted to the rear of
the catalyst system. The main drawbacks with urea
SCR are urea availability, and ensuring the compli-
ance of the vehicle operator. A system known as
SCRTs, with urea SCR following a CRTs, for the
removal of PM, CO, hydrocarbon, and NOx from
diesel exhaust, is shown in Fig. 4.
 Cleaner Vehicle Emissions

Another catalyst technology available for NOx complex engine design and operation, and also results
removal is the LNT, also called NOx adsorber in a fuel penalty that must be minimized.
catalyst, DeNOx trap, NOx storage catalyst, or
NOx storage/reduction catalyst. The final LNT
catalyst is similar to a TWC catalyst in appearance (a) Lean operation. NO oxidation
and washcoat composition. The catalyst comprises Pt
and Rh supported on g-Al2O3, and a NOx storage 2NOðgÞ þ O2 ðgÞ"2NO2
component. The common materials for NOx storage
are oxides of barium, strontium, cesium, or potas-
sium. By choosing the appropriate storage materials Storage of NO2 as nitrate
or a combination of them (based on NOx storage
capacity and thermal stability), it is possible to tune MO þ 2NO2 þ 12O2 -MðNO3 Þ2 ð18Þ
the performance of the LNT for different engines,
vehicles and applications, that is, different engine
operating temperatures. The NOx trap operates by (b) Regeneration (rich operation). Nitrate reduc-
storing NOx under normal, lean-burn operating tion by CO
conditions, and then releasing and reducing the
NOx during a brief periodic rich pulse. This requires MðNO3 Þ2 þ 3CO-MO þ 2NO þ 3CO2 ð19Þ

NH
3 +N
Ox
→
N
ASC 2+
H
2O

SC
R
ca
tal
ys
t

DO
C

DP
F

PM
+N NO
O
2 → +½
CO O
/C 2 →
O NO
2 +
NO 2

© Copyright Jonson Mathey Pic 2005

Urea soln.
Figure 4
SCRTs system incorporating particulate filtration, urea SCR, and ASC (present as a stripe at the rear of the SCR
catalyst). Adapted from Ahmadinejad M, Desai M R, Watling T C, York A P E 2008 Simulation of automotive
emission control systems. Adv. Chem. Eng. 33, 47–101, with permission from Elsevier.

5
Cleaner Vehicle Emissions

Table 1
Disadvantages of the SCR and NOx trap catalyst systems.

Urea selective catalytic reduction Lean NOx trap

Need separate reductant Complex engine design and operation for periodic rich
 Driver compliance cycles. Oil dilution occurs during regeneration.
 Widespread availability
NH3 slip Cost: PGM based
Unselective reactions
 2NH3 þ 2O2 ¼ N2O þ 3H2O: N2O is a pollutant SOx trapped more strongly than NOx, thus leading to loss
in performance. It requires periodic high-temperature
desulfation
 4NH3 þ 3O2 ¼ 2N2 þ 6H2O: wastes NH3 Regeneration results in fuel penalty (lower fuel economy).
 4NH3 þ 5O2 ¼ 4NO þ 6H2O: produces NO Engine management to control lean-rich cycling and
model stored NOx.

Nitrate reduction by H2 preparation procedure, and by including hydrocar-

MðNO3 Þ2 þ 3H2 -MO þ 2NO þ 3H2 O ð20Þ
Nitrate reduction by HC
MðNO3 Þ2 þ 13C3 H6 -MO þ 2NO þ H2 O þ CO2 ð21Þ
NO reduction (CO)
2NOðgÞ þ 2COðgÞ-2CO2 ðgÞ þ N2 ðgÞ
NO reduction (H2)
2NOðgÞ þ 2H2 ðgÞ-N2 ðgÞ þ 2H2 OðgÞ
LNT catalyst technology also requires low sulfur
fuel to operate effectively since sulfates, formed by
reaction of SO3 with the metal oxide, are more stable
than the nitrates, resulting in catalyst deterioration.
This loss in catalyst performance can be reversed by
high-temperature desulfation. Urea SCR and LNT
systems are compared in Table 1.
A less-well-developed alternative for NOx control
is hydrocarbon SCR, where NOx is converted to N2
under lean exhaust conditions by reaction with
hydrocarbons (fuel) in the presence of a solid catalyst
(reaction (12)). Various catalysts have been studied in
this respect, including Cu supported on zeolite, Ag,
Pt, In, and Ga supported on alumina. Each catalyst,
depending on the type of HCs and preparation
procedure, exhibits good activity in a different
temperature window. It has become clear that Ag/
Al2O3 has several advantages over other potential
diesel-SCR catalysts. It has low activity for SO2
oxidation (a common step in catalyst sulfation and
loss of the SCR activity), relatively high thermal and
hydrothermal durability (compared to Cu/ZSM5),
high selectivity to N2 (unlike Pt-based catalysts which
form measurable amounts of N2O), and is relatively
cheaper compared to precious metals. Its major
disadvantage is its poor activity below 3501C with
diesel fuel. This limitation can be partially overcome
by controlling the fuel:NOx ratio, modifying catalyst
bon-activating components in the catalyst formula-
tion. Under an optimized HC:NOx ratio, when diesel
fuel is used as reductant, the presence of a very small
amount of H2 (less than 1000 ppm) is capable of
substantially improving the performance of the Ag/
Al2O3 HC-SCR catalyst.
A guide to typical emissions control aftertreatment
catalyst performance, for the catalysts discussed
herein, is given in Table 2. Improved performance
can be achieved by system design.
4. Future Challenges and Advances in Catalyst
Technology
Vehicle and engine manufacturers are faced with the
challenge of simultaneously improving efficiency and
pollutant emissions, a trade-off that is difficult to
achieve using conventional technologies. These chal-
lenges are also extending to new markets, for
example, locomotives, marine, and nonroad mobile
machinery (e.g., farm and construction). Develop-
ment strategies will continue to be focused in three
main areas, which are discussed below.
4.1 Engine Technology
New engine designs will include incorporating direct
injection, downsized turbocharging, lean burn, and
homogeneously charged compression ignition. In
addition, dual-fuelled vehicles may become more
popular (e.g., gasoline/ethanol).
4.2 Fuels
The use of biofuels (e.g., fatty acid methyl ester
biodiesel or ethanol), synthetic fuels (derived from
coal or natural gas), and blends of these with
conventional fuels is on the increase, and this trend

6

Table 2
Guideline to individual catalyst performance for a
standard drive cycle representative of real-world driving.
Conversion
CO Hydrocarbon NOx
TWC 490% 490% 495%
DOC 490 490 p15%
Urea SCR 70% to 490%
HC SCR p50%
LNT 480% 480% 60–80%
is likely to continue in the future. Further, hydrogen
produced from renewable sources, that is, biomass
waste, wind, or solar power, could become more
popular, both in new powertrain types, for example,
fuel cells (see Solid Oxide Fuel Cells), and also in IC
engines. However, there are still hydrogen storage
and distribution challenges, although low hydrogen
concentrations could be produced on-board the
vehicle using, for example, catalytic/plasma fuel
reforming or electrolysis, to supplement to the engine
main fuel.
4.3 Catalyst Technology
Significant progress has been made in developing
aftertreatment technologies and the catalytic materi-
als required. This has resulted in the design of more
efficient, durable, lightweight, compact, and cost-
effective aftertreatment devices (e.g., removing/redu-
cing Rh content in TWCs). Examples of recent
developments, and those that may be seen in the
future, are:
(i) Combining catalyst and filter functions into one
device, resulting in a multi-functional catalyst. Exam-
ples are the catalyzed DPF, including DOC function,
and the Toyota diesel particulate NOx reduction
(DPNR) catalyst combining DPF and LNT.
(ii) Catalyst zoning, in which the catalyst loading
can vary along the length of the catalyst system. In this
way, it is possible to improve the emissions control
performance, maintain longer-term stability, and
reduce costs considerably. Zoning could equally be
used in the manufacture of catalyst and filter systems,
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Encyclopedia of Materials: Science and Technology
Cleaner Vehicle Emissions
for example, DOC, or even by zoning different
catalysts into different parts of the catalyst substrate.
(iii) The development of multifunctional catalysts
by layering the individual catalysts, for example,
layering a NOx trap/SCR system, giving potentially
improved performance over a wider operating window.
In reality, a combination of technological advances is
required to meet the evermore stringent regulations,
with catalytic aftertreatment systems at the fore-
front. The challenges will be designing aftertreatment
systems to operate successfully with such a wide
range of engines, fuels, and vehicles.
See also: Catalysis; Supported Catalysts; Platinum
Group Metals: Alloying, Properties, and Applica-
tions; Heterogeneous Catalysis: Use of Density
Functional Theory; Solid Oxide Fuel Cells.
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