Cleaner Vehicle Emissions needed, and, for this purpose, air was injected into

the exhaust gas.

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

1
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 cordierite (2MgO  2Al2O3  5SiO2), but they can also
be formed from stainless steel; a typical cordierite
The catalyst is coated onto the walls of the monolith monolith has 400 channels in  2 (64 channel openings
material in the form of a slurry material, known as cm  2), but can also come with 900 cm  2 or even
washcoat, leading to a thin, porous catalyst layer (30– 1200 cm  2. Cordierite is used as it has a low
150 mm) within the monolith. These monoliths are coefficient of thermal expansion and can therefore
often formed from a ceramic material, known as withstand the high heating rates encountered when

2
 Cleaner Vehicle Emissions

the engine first starts—typically, the exhaust gas in design, have lead to a rise in the popularity of
temperature can reach several hundred degrees in less diesel vehicles over the past 10 years or so, especially
than a minute. Metallic monoliths tend to be used in Europe.
when the space on the vehicle is limited since the In a diesel engine, the required amount of fuel is
monolith can be welded directly into the exhaust. The injected into an excess of air in the engine cylinder.
washcoat containing all the parts of the catalyst is The resulting exhaust gas therefore still contains a
typically composed of: large amount of oxygen; thus, TWCs, which rely on a
(i) catalyst support material, for example, g-Al2O3; stoichiometric mixture, cannot be employed for diesel
(ii) catalyst stabilizers/promoters, for example, pollution control. Diesel aftertreatment can be
BaO, La2O3; divided into three loose categories:
(iii) active constituents of the catalyst, typically (i) catalysts for oxidation, that is, hydrocarbon
platinum and/or palladium, and rhodium; and and CO removal;
(iv) oxygen storage component, ceria (CeO2). (ii) catalysts and filters for PM removal; and
(iii) catalysts for NOx abatement.
The exact formulation depends on many factors,
such as the vehicle type, the market, legislation, metal Usually, a combination of catalysts is required for
prices, and so on. Platinum group metals (PGMs) are removal of all the pollutants, for example, putting a
used because they are very tolerant to poisons, for filter in series to remove PM, followed by selective
example, sulfur, present in vehicle exhausts (com- catalytic reduction (SCR), for NOx control.
pared with base metals); without any external
damage, these catalysts usually operate successfully
for periods beyond the lifetime of the vehicle or for 3.1 Diesel Oxidation Catalysts
periods determined by the legislated time/mileage. A diesel oxidation catalyst (DOC) is employed to
The Pt, Pd, and Rh are very expensive. However, remove CO and hydrocarbons using the oxygen in
they only make up a tiny fraction of the total the exhaust (5–15% of the gases). It also oxidizes NO
washcoat, for example, 1%. to NO2, which, if left unchecked, results in elevated
The addition of ceria to the catalyst is necessary to levels of NO2 at the exhaust pipe exit. In practice, this
improve the conversion of hydrocarbon, CO, and is controlled by defining the appropriate catalyst
NOx. This is because, despite the excellent control of formulation, size, and PGM loading.
the A/F ratio, fluctuation still occurs, though only Hydrocarbon oxidation, for example
slightly to each side of the stoichiometric point. Ceria
can store oxygen in the exhaust in its lattice under C12 H26 ðgÞ þ 1812O2 ðgÞ-12CO2 ðgÞ þ 13H2 OðgÞ ð10Þ
fuel-lean conditions, promoting the reduction of NOx
to N2, and then use this oxygen to oxidize hydro- NO oxidation
carbons and CO under fuel-rich conditions. In this
way, ceria dampens the variations in the A/F ratio 2NOðgÞ þ O2 ðgÞ"2NO2 ð11Þ
and improves the catalyst performance over a wider
window of operating conditions: Furthermore, NOx abatement technology can be
used to address this problem, and, indeed, NO2
2CeO2 þ CO-Ce2 O3 þ CO2 ð8Þ formation over a DOC is an essential part of some
diesel aftertreatment systems. DOCs are usually
washcoated onto ceramic monoliths, as is the case
Ce2 O3 þ 12O2 -2CeO2 ð9Þ for the TWC. Typical washcoats are made up of the
support material, for example, g-Al2O3, and the
Ceria also enhances the WGS activity of Pt–Rh active metal component, which can be Pt and/or Pd.
TWCs, and hence promotes CO removal under fuel- Under certain conditions, DOCs can also contribute
rich conditions; in addition, it can act as a structural a small NOx reduction function to their performance
promoter, stabilizing the precious metals and alumi- by using the hydrocarbon present; typically, this is
na against sintering and particle growth. low and only occurs over a narrow temperature
range.
NO reduction (HC)
3. Diesel or Lean-burn Engines
 m  m
Diesel engines have several advantages compared to Cn Hm ðgÞ þ 2n þ NOðgÞ- n þ N2 ðgÞ þ nCO2 ðgÞ
2 m4
petrol engines, that is, high torque, fuel economy (low
CO2), durability, and ability to use a range of fuels. þ H2 OðgÞ ð12Þ
2
However, due to their image (noisy, dirty, heavy, and
low performance) in the past they were mainly used A further function, improving the hydrocarbon
in nonroad and heavy-duty vehicle applications. performance, can be added to the DOC by including
Concerns over global warming, and improvements zeolites. These adsorb hydrocarbons when the

3
Cleaner Vehicle Emissions

catalyst is cold, that is, at ‘‘cold start’’ immediately oxidation rate is 500–5501C, far above that observed
after start up. The hydrocarbons are then desorbed in typical diesel exhausts (200–3001C). Therefore,
and oxidized as the temperature increases to that extra heat is provided, usually by injecting hydro-
required for catalytic oxidation to occur. 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
3.2 Diesel PM Control temperature since a runaway reaction can lead to
irreversible filter damage. Furthermore, active meth-
The most successful and widely used materials for ods result in a fuel penalty.
PM emission control are wall-flow filters, also known
as diesel particulate filters (DPFs). Typically con-
structed from cordierite, silicon carbide (SiC), or 3.3 Diesel NOx Removal Catalyst Technology
aluminum titanate (Al2TiO5), these devices capture Catalytic NOx removal from the diesel exhaust is
the PM in their porous wall structure as the gas is usually achieved by either the addition of a separate
forced through the wall from the inlet channel to reductant, in SCR, or by engine/combustion manage-
outlet channel (Fig. 3). At their simplest level, the ment using a lean NOx trap (LNT).
filters are bare and not coated with a catalyst; Urea/ammonia SCR is a process in which NOx is
however, multifunctional systems can be devised by reduced by ammonia, typically introduced as a urea
adding a catalyst, for example, DOC, or a NOx solution (Adblue, 32.5% aqueous solution) sprayed
abatement catalyst. into the exhaust upstream of the catalyst. Typical
To maintain the long-term operation of the filters, catalysts for urea SCR include supported vanadium
it is necessary to remove the filtered PM. This can be oxide (V2O5), and iron or copper supported on
done using passive regeneration, which is a continual zeolite, which is washcoated onto a monolith (as for
process, or periodic active regeneration (or both). In the TWC).
a passive system, the NO2 in the exhaust is used to Urea decomposition
oxidize the PM to CO and (mainly) CO2. To
maximize the NO2 content in the exhaust gas, a NH2 CONH2 -NH3 þ HNCO ð13Þ
DOC is used upstream to convert NO to NO2; this is Hydrolysis
the basis of the very successful Continuously
Regenerating Trap (CRTs) system. Even greater HNCO þ H2 O-NH3 þ CO2 ð14Þ
passive regeneration performance can be achieved by
adding a Pt catalyst to the filter; this is the Catalyzed NO SCR
CRT (CCRTs) device. However, in some cases,
4NH3 þ 4NO þ O2 -4N2 þ 6H2 O ð15Þ
passive regeneration cannot be used, for example, not
enough NOx available or the temperature being too NO2 SCR
low. In this case, active regeneration, using oxygen in
the exhaust, is periodically applied to the system. 8NH3 þ 6NO2 -7N2 þ 12H2 O ð16Þ
However, the temperature required for a useful PM
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
Figure 3 the catalyst system. The main drawbacks with urea
A schematic showing the operating principle of a wall- SCR are urea availability, and ensuring the compli-
flow filter. Courtesy of Corning Inc. Reproduced from ance of the vehicle operator. A system known as
Twigg M V 2007 Progress and future challenges in SCRTs, with urea SCR following a CRTs, for the
controlling automotive exhaust gas emissions. Appl. Catal. removal of PM, CO, hydrocarbon, and NOx from
B: Environ. 70, 2–15, with permission from Elsevier. diesel exhaust, is shown in Fig. 4.

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

6
 Cleaner Vehicle Emissions

Table 2 for example, DOC, or even by zoning different

Guideline to individual catalyst performance for a catalysts into different parts of the catalyst substrate.
standard drive cycle representative of real-world driving. (iii) The development of multifunctional catalysts
by layering the individual catalysts, for example,
Conversion layering a NOx trap/SCR system, giving potentially
improved performance over a wider operating window.
CO Hydrocarbon NOx In reality, a combination of technological advances is
required to meet the evermore stringent regulations,
TWC 490% 490% 495% with catalytic aftertreatment systems at the fore-
DOC 490 490 p15%
front. The challenges will be designing aftertreatment
Urea SCR 70% to 490% systems to operate successfully with such a wide
HC SCR p50% range of engines, fuels, and vehicles.
LNT 480% 480% 60–80%

is likely to continue in the future. Further, hydrogen See also: Catalysis; Supported Catalysts; Platinum
produced from renewable sources, that is, biomass Group Metals: Alloying, Properties, and Applica-
waste, wind, or solar power, could become more tions; Heterogeneous Catalysis: Use of Density
popular, both in new powertrain types, for example, Functional Theory; Solid Oxide Fuel Cells.
fuel cells (see Solid Oxide Fuel Cells), and also in IC
engines. However, there are still hydrogen storage Bibliography
and distribution challenges, although low hydrogen Ahmadinejad M, Desai M R, Watling T C, York A P E 2008
concentrations could be produced on-board the Simulation of automotive emission control systems. Adv.
vehicle using, for example, catalytic/plasma fuel Chem. Eng. 33, 47–101
reforming or electrolysis, to supplement to the engine Burch R (ed.) 2004 Scientific and technical developments in
main fuel. automotive emissions control since the 1970s. Top. Catal. 28,
1–202
Chatterjee S, Walker A P, Blakeman P G 2008 Emission control
4.3 Catalyst Technology options to achieve Euro IV and Euro V on heavy duty diesel
engines. SAE -28-0021, 136–48
Significant progress has been made in developing Cooper B J, Jung H J, Thoss J E 1990 Treatment of diesel
aftertreatment technologies and the catalytic materi- exhaust gases. US Patent No. 4 902 487
als required. This has resulted in the design of more Gandhi H S, Graham G W, McCabe R W 2003 Automotive
efficient, durable, lightweight, compact, and cost- exhaust catalysis. J. Catal. 216, 433–42
effective aftertreatment devices (e.g., removing/redu- Heck R M, Farrauto R J 2001 Automobile exhaust catalysts.
cing Rh content in TWCs). Examples of recent Appl. Catal. A: Gen. 221, 443–57
developments, and those that may be seen in the Heck R M, Farrauto R J, Gulati S T 2009 Catalytic Air
Pollution Control: Commercial Technology, 3rd edn. Wiley,
future, are: New York
(i) Combining catalyst and filter functions into one Johnson T 2008 Diesel engine emissions and their control.
device, resulting in a multi-functional catalyst. Exam- Platinum Met. Rev. 52, 23–37
ples are the catalyzed DPF, including DOC function, Lapuerta M, Armas O, Rodr!ıguez-Fern!andez J 2008 Effect of
and the Toyota diesel particulate NOx reduction biodiesel fuels on diesel engine emissions. Prog. Energ.
(DPNR) catalyst combining DPF and LNT. Combust. Sci. 34, 198–223
(ii) Catalyst zoning, in which the catalyst loading Stone R 1999 Introduction to Internal Combustion Engines, 3rd
can vary along the length of the catalyst system. In this edn. Palgrave, New York
way, it is possible to improve the emissions control Twigg M V 2007 Progress and future challenges in controlling
automotive exhaust gas emissions. Appl. Catal. B: Environ.
performance, maintain longer-term stability, and 70, 2–15
reduce costs considerably. Zoning could equally be
used in the manufacture of catalyst and filter systems,
A. P. E. York and A. Tsolakis

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