C261etukansi.

fm Page 1 Tuesday, November 21, 2006 10:18 AM

OULU 2006

C 261
C 261

ACTA
UNIVERSITY OF OULU P.O. Box 7500 FI-90014 UNIVERSITY OF OULU FINLAND

ACTA
U N I V E R S I T AT I S O U L U E N S I S

C
A C TA U N I V E R S I TAT I S O U L U E N S I S

S E R I E S E D I T O R S
Mika Huuhtanen TECHNICA

ASCIENTIAE RERUM NATURALIUM

ZEOLITE CATALYSTS IN

Mika Huuhtanen
Professor Mikko Siponen

BHUMANIORA THE REDUCTION OF NOX IN

LEAN AUTOMOTIVE EXHAUST
Professor Harri Mantila

CTECHNICA
Professor Juha Kostamovaara GAS CONDITIONS
DMEDICA
Professor Olli Vuolteenaho BEHAVIOUR OF CATALYSTS IN ACTIVITY,
DRIFT AND TPD STUDIES
ESCIENTIAE RERUM SOCIALIUM
Senior Assistant Timo Latomaa

FSCRIPTA ACADEMICA
Communications Officer Elna Stjerna

GOECONOMICA
Senior Lecturer Seppo Eriksson

EDITOR IN CHIEF
Professor Olli Vuolteenaho
EDITORIAL SECRETARY
Publications Editor Kirsti Nurkkala FACULTY OF TECHNOLOGY,
DEPARTMENT OF PROCESS AND ENVIRONMENTAL ENGINEERING,
UNIVERSITY OF OULU
ISBN 951-42-8285-X (Paperback)
ISBN 951-42-8286-8 (PDF)
ISSN 0355-3213 (Print)
ISSN 1796-2226 (Online)
ACTA UNIVERSITATIS OULUENSIS
C Te c h n i c a 2 6 1

MIKA HUUHTANEN

ZEOLITE CATALYSTS IN
THE REDUCTION OF NOX
IN LEAN AUTOMOTIVE EXHAUST
GAS CONDITIONS
Behaviour of catalysts in activity, DRIFT and
TPD studies

Academic dissertation to be presented, with the assent of

the Faculty of Technology of the University of Oulu, for
public defence in Auditorium TA105, Linnanmaa,
on December 1st, 2006, at 12 noon

O U L U N Y L I O P I S TO, O U L U 2 0 0 6
Copyright © 2006
Acta Univ. Oul. C 261, 2006

Supervised by
Professor Riitta L. Keiski

Reviewed by
Docent Narendra Kumar
Doctor Antonio E. Palomares Gimeno

ISBN 951-42-8285-X (Paperback)

ISBN 951-42-8286-8 (PDF) http://herkules.oulu.fi/isbn9514282868/
ISSN 0355-3213 (Printed)
ISSN 1796-2226 (Online) http://herkules.oulu.fi/issn03553213/

Cover design
Raimo Ahonen

OULU UNIVERSITY PRESS

OULU 2006
Huuhtanen, Mika, Zeolite catalysts in the reduction of NOx in lean automotive
exhaust gas conditions. Behaviour of catalysts in activity, DRIFT and TPD studies
Faculty of Technology, University of Oulu, P.O.Box 4000, FI-90014 University of Oulu, Finland,
Department of Process and Environmental Engineering, University of Oulu, P.O.Box 4300, FI-
90014 University of Oulu, Finland
Acta Univ. Oul. C 261, 2006
Oulu, Finland

Abstract
The aim of the thesis is to expand the knowledge of the catalytic properties of platinum-loaded zeolite
catalysts in the reduction of NOx by hydrocarbons. The work is divided into three parts. First the
recent literature of zeolite catalysts has been introduced, secondly the adsorption capacity, activity,
and acidity of the catalysts have been studied by TPD and IR techniques, and thirdly the derived
reaction mechanisms based on the obtained data are presented.
Parent and 1 wt-% Pt-loaded ZSM-5, Beta, Y, and Ferrierite zeolite catalysts have been studied in
the C3H6-assisted reduction of NO. The Pd/Al2O3-based catalyst was used as a reference material for
the reaction mechanistic studies. Several experimental techniques (in situ DRIFT, activity
measurements, CO chemisorption, N2 physisorption, TPD, and TEM) have been used for the
characterisation of the catalysts properties. The IR technique was used as the main technique for the
determination of activities, surface species, and the acidic properties of the zeolite-based catalysts.
The activity studies carried out by the gaseous FTIR technique provide information on the desired
reaction products as well as the undesired by-products. The detection and identification of the surface
species as well as the reaction intermediates formed were done by the DRIFT method.
The activity experiments indicate the effectiveness of the Pt-loaded zeolite catalysts. The
reduction of NO was found to decrease in the order: Pt/Beta > Pt/Y > Pt/Ferrierite > Pt/ZSM-5 in the
conditions with excess O2. Platinum can be concluded to have an effect on O2 and NO dissociation.
Oxidation reactions of NO to NO2 and propene to CO2 were observed to be more intense over the
platinum-loaded zeolites than over the parent zeolites.
In this work the reaction mechanisms for the C3H6-SCR of NO were derived over the Pt-loaded
zeolite as well as the Pd/alumina catalysts based on the data obtained by DRIFT and activity
experiments. The kinetics for the NO reduction by CO over Pd/Al2O3 was also derived. With the
methods employed, the mechanistic steps over the Pt-loaded zeolites and Pd/Al2O3-based catalysts
could be derived quite precisely and easily for C3H6-SCR of NO. Reaction routes were determined
to go via different formations of intermediates over the two catalysts, i.e. via organonitrogen and
isocyanate routes, respectively. The IR techniques were discovered to be effective tools in applied
engineering studies.

Keywords: acidity, aluminium oxide catalysts, catalyst activity, characterisation, infrared

techniques, palladium, platinum, reaction mechanisms, temperature programmed
desorption, zeolite catalysts
 Acknowledgements
The study reported in this thesis was carried out in the Department of Process and
Environmental Engineering at the University of Oulu (OU) during the years 2001-2006.
First of all, I would like to express my most sincere gratitude to my supervisor
Professor Riitta L. Keiski, the Head of the Laboratory for her encouragement and
guidance during this work as well as for the opportunity to work in her group.
I am grateful to Ecocat Oy (formerly Kemira Metalkat Oy) for providing the catalytic
materials studied. I would like to acknowledge my co-authors: M.Sc.(Eng.) Teuvo
Maunula and D.Tech. Katariina Rahkamaa-Tolonen from Ecocat Oy, as well as D.Tech.
Tanja Kolli, Lic.Tech. Juha Ahola and M.Sc.(Eng) Tomi Määttä (OU).
Many thanks for the help with the experimental work to Mr. Jorma Penttinen (OU) and
Ms. Sirkka Ervasti (Ecocat Oy).
I would also like to thank Doc. Narendra Kumar (Åbo Akademi University) and Dr.
Antonio Eduardo Palomares Gimeno (Universidad Politecnica de Valencia) for reviewing
the manuscript of my thesis. Mr. Keith Hakso is acknowledged for linguistic corrections.
Special thanks to all my colleagues in Mass and Heat Transfer Process Laboratory for
the pleasant working atmosphere.
Finally, I want to express my warmest thanks to my mother Helka and sister Kirsi for
the encouragement and support throughout my studies. I like also to thank my beloved,
Marja for her assistance.
The financial support of the Academy of Finland, the Maj and Tor Nessling
Foundation, the Henry Ford Foundation and TES foundation are greatfully
acknowledged.
Oulu, 30 October 2006 Mika Huuhtanen
 List of symbols and abbreviations

Latin letters
ci Concentration of the component i, mol/dm3
Ea, i Energy of activation for component i, kJ/mol
Fi Molar inlet rate of component i, mol/s
ΔGf0 Gibbs energy, kJ/mol
Hi Enthalpy, kJ/mol
h Hour(s)
k Reaction rate constant, (different units, see Table 10)
Ki Equilibrium constant, m3/mol
l Length, m
mcat Catalyst mass, g
ri Reaction rate, mol/g s
R2 Regression determination coefficient, %
SBET Specific surface area by BET method, m2g-1
T Temperature, ºC, K
T50 Temperature when conversion reaches 50%, °C
v Gas velocity, cm3/h
xi Fractional conversion of component i, (dimensionless)
Xi Conversion of component i, %
Å Ångström, 1×10-10 m
Abbreviations
AAS Atomic absorption spectroscopy
A/F Air-to-fuel-ratio. In stoichiometry A/F = 14.7
BET Brunauer-Emmett-Teller -theory
BJH Barrett-Joyner-Halenda -theory
cpsi Cell per square inch, 1/in2
DI Direct injection
DRIFT(S) Diffuse Reflectance Infrared Fourier Transform (Spectroscopy)
EC European Commission
EDS Energy Dispersive Spectroscopy
EFTEM Energy-Filtered Transmission Electron Microscopy
EU European Union
Euro 1-5 European Union Emission Standards, stages 1-5
FTIR Fourier Transform Infrared Spectroscopy
GHSV Gas Hourly Space Velocity
HC Hydrocarbon
HC-SCR Hydrocarbon-assisted Selective Catalytic Reduction
IR Infrared
LEV II Californian Low Emission Vehicle standard II
NMHC Non-methane hydrocarbons
NOX Nitrogen oxides, NO, NO2, N2O
OBD On-Board Diagnostics
ODE Ordinary Differential Equation
PGM Platinum group metals (Pt, Pd, Rh, Ru, Os, Ir)
PyB Brønsted acid site
PyL Lewis acid site
SCR Selective Catalytic Reduction
TEM Transmission Electron Microscopy
TPD Temperature Programmed Desorption
TWC Three-Way Catalyst
 List of original papers
This thesis is based on the following publications, which are referred to in the text by
their Roman numerals:
I Huuhtanen M, Määttä T, Rahkamaa-Tolonen K, Maunula T & Keiski RL (2004)
Adsorption of propene in the presence and absence of oxygen or nitric oxide on Pt-
loaded ZSM-5, Beta, Y and Ferrierite zeolites. Topics in Catalysis 30/31: 359-363.
II Huuhtanen M, Rahkamaa-Tolonen K, Maunula T & Keiski RL (2005) Pt-loaded
zeolites for reducing exhaust gas emissions at low temperatures and in lean
conditions. Catalysis Today 100(3-4): 321-325.
III Huuhtanen M, Maunula T & Keiski RL (2005) Reaction mechanism for C3H6-SCR
of NO over a Pt loaded ZSM-5 zeolite catalyst. Studies in Surface Science and
Catalysis 158: 1867-1874.
IV Ahola J, Huuhtanen M & Keiski RL (2003) Integration of in situ FTIR studies and
catalyst activity measurements in reaction kinetic analysis. Industrial Engineering &
Chemical Research 42(12): 2756-2766.
V Huuhtanen M, Kolli T, Maunula T & Keiski RL (2002) In situ FTIR study on NO
reduction by C3H6 over Pd-based catalysts. Catalysis Today 75(1-4): 379-384.
The manuscripts for the publications (Papers I-III and V) were written by the author of
this thesis. In Paper IV the experiments and data analyses were the author’s contribution
and the manuscript was written in close collaboration with the first author.
 List of tables
Table 1. EU emission standards for gasoline passenger cars (g/km)
(Dieselnet_EU 2005, ACEA 2004, Burch 2004, EU 2005). ...................... 18
Table 2. Typical exhaust gas compositions of gasoline and diesel engines
(Heck & Farrauto 2001, Gabrielsson 2004, Roduit et al. 1998,
Kašpar et al. 2003, Tabata et al. 1995)....................................................... 23
Table 3. Experimental conditions in activity measurement over the 1 wt-%
Pt/zeolite catalysts...................................................................................... 32
Table 4. Measured specific surface areas, average pore sizes, pore
volumes, and platinum dispersions of the ZSM-5, Beta, Y, and
Ferrierite zeolite-based catalysts studied.................................................... 37
Table 5. Maximum by-product (CO, N2O, and NO2) concentrations
measured in the NO+C3H6+O2 reaction gas mixture on parent and
1 wt-% Pt-loaded ZSM-5, Beta, Y, and Ferrierite catalysts........................ 44
Table 6. The observed reaction intermediates and products for NO, C3H6,
and/or O2 reactions (1 and 3% Pd-catalysts); reaction mechanism
approach (Paper V). ................................................................................... 61
Table 7. The reaction mechanistic approach for NO reduction by CO
(Paper IV). ................................................................................................. 62
Table 8. Identified surface and free intermediate species over 1 wt-%
Pt/ZSM-5 under reaction conditions (1000 ppm NO, 1000 ppm
C3H6, and 5% O2); comparison with the literature data (Paper III)............ 63
Table 9. The possible mechanistic steps for the C3H6-SCR of NO over Pt-
zeolite catalysts. ......................................................................................... 65
Table 10. The calculated parameters for the kinetic models of NO reduction
by CO in the three mechanisms studied (see Table 7)................................ 68
 List of figures
Fig. 1. Current and subsequent stage of the emission standards in the EU,
USA Federal, and Japan (Dieselnet_USA 2004, Walsh 1999, EPA
2000, EPA 2002). ....................................................................................... 19
Fig. 2. Conversions of hydrocarbons, CO, and NO by three-way catalysts
(Reprinted from Appl. Catal. A 221, Heck & Farrauto, 2001 with
the permission of Elsevier). ....................................................................... 22
Fig. 3. Structures of the a) ZSM-5, b) Beta, c) Y, and d) Ferrierite zeolites
(Redrawn from Baerlocher and McCusker 2000). ..................................... 28
Fig. 4. Schematic figure of packaging the catalyst samples into the
tubular reactor. ........................................................................................... 31
Fig. 5. Experimental set-up for the activity measurements ................................... 33
Fig. 6. Schematic figure of the experimental set-up for DRIFT studies................ 34
Fig. 7. Photograph of the TPD experimental set-up. ............................................. 35
Fig. 8. N2 adsorption and desorption isotherms of Pt-loaded ZSM-5, Beta,
Y and Ferrierite zeolites. ............................................................................ 37
Fig. 9. TEM images of the Pt clusters on the a) ZSM-5, b) Beta, c) Y, and
d) Ferrierite zeolite surfaces, respectively. Black particles indicate
the Pt clusters and the dark grey form are due to the zeolite
support. Magnification: ¯100 000. ........................................................... 38
Fig. 10. Example of the EDS spectra (1 wt-% Pt-loaded ZSM-5 zeolite
catalyst)...................................................................................................... 38
Fig. 11. a) NO and b) C3H6 conversions and light-off temperatures of Pt-
loaded zeolites with a reaction gas mixture of 1000 ppm NO, 1000
ppm propene, balanced by N2. ................................................................... 40
Fig. 12. a) NO and b) C3H6 conversions and light-off temperatures of Pt-
loaded zeolites with a reaction gas mixture of 1000 ppm NO, 1000
ppm propene, and 5% oxygen balanced by N2 (Paper II). ......................... 41
Fig. 13. NO conversions in the absence and presence of excess oxygen
over the Pt-loaded catalysts........................................................................ 42
Fig. 14. Comparison of the light-off temperatures of propene over the
parent and Pt-loaded zeolite catalysts (1000 ppm NO, 1000 ppm
C3H6, 5% O2)............................................................................................. 43
Fig. 15. Comparison of the conversions of NO and propene over the parent
(S and U) and Pt-loaded ZSM-5 (… and —) zeolite catalysts
(Paper III)................................................................................................... 44
Fig. 16. An example of the concentrations of reactants and products as a
function of temperature in lean conditions, 5000 ppm NO, 400
ppm C3H6, over 1% Pd/Al2O3. The N2 concentration is a
calculated value. (Paper V) ........................................................................ 47
Fig. 17. DRIFT spectra of adsorbed surface species over 1 wt-% Pt/ZSM-5
as a function of temperature. Reaction gas mixture: 1000 ppm NO
+ 1000 ppm C3H6 + 5 vol-% O2. (Paper III) .............................................. 48
Fig. 18. DRIFT spectra of adsorbed surface species over parent and Pt-
loaded zeolites at a temperature of 100ºC. Reaction gas mixture:
1000 ppm C3H6 + 5 vol-% O2. (Paper I) .................................................... 50
Fig. 19. The spectra of NO + C3H6 reaction on 1 wt-% Pd/Al2O3 catalysts
at 260°C in fuel rich, stoichiometric, and lean conditions with
excess O2 conditions. The NO+O2 spectrum is also shown. (Paper
V) ............................................................................................................... 51
Fig. 20. TPD study of NO desorption over parent and Pt-loaded zeolites.
In the interior graph desorption over the parent and Pt-loaded Y
and Ferrierite zeolites is presented in detail. (Paper I) ............................... 52
Fig. 21. Propene desorption bands over the parent and 1 wt-% Pt-loaded
zeolites. A C3H6+O2-TPD study. In the interior graph desorption
over the parent and Pt-loaded Y and Ferrierite zeolites is presented
in detail. (Paper I)....................................................................................... 53
Fig. 22. Comparison of the calculated desorption amounts of NO and C3H6
during the NO-, C3H6-, and C3H6 + O2 -TPD experiments (Paper
I)................................................................................................................. 53
Fig. 23. DRIFT spectra of pyridine adsorption over the parent ZSM-5 (a),
Beta (b), Y (c) and the 1 wt-% Pt-loaded ZSM-5 (d), Beta (e) and
Y (f) zeolites. Spectra have been taken after (I) pyridine
adsorption at 150°C for 4 minutes, (II) evacuation at 150°C for 30
minutes, (III) evacuation at 250°C for 60 minutes, and (IV)
evacuation at 350°C for 60 minutes. .......................................................... 56
Fig. 24. A plausible reaction mechanism for the C3H6-SCR of NOX over
Pt-loaded zeolite catalysts (Paper III). ....................................................... 66
Fig. 25. Example of the experimental CO (∗), NO (×) and N2O (V)
concentrations and the calculated values (solid line) of the direct
decomposition model (A) in lean a) NO-CO and b) NO+CO+O2
conditions................................................................................................... 69
 Contents
Abstract
Acknowledgements
List of symbols and abbreviations
List of original papers
List of tables
List of figures
Contents
1 Introduction ................................................................................................................... 17
1.1 General ...................................................................................................................17
1.2 Selective catalytic reduction (SCR)........................................................................19
1.3 Scope and aims of the research...............................................................................20
2 Lean gasoline and diesel conditions .............................................................................. 22
2.1 Hydrocarbon-assisted reduction of NOX ................................................................23
2.2 Abatement of NOX by other reductants ..................................................................25
3 Catalyst materials .......................................................................................................... 27
3.1 Zeolite catalysts ......................................................................................................27
3.1.1 General ............................................................................................................27
3.1.2 Pt/zeolite catalyst preparation..........................................................................28
3.2 Alumina-based materials ........................................................................................29
3.2.1 General ............................................................................................................29
3.2.2 Pd/Al2O3 catalyst preparation ..........................................................................29
4 Experimental ................................................................................................................. 30
4.1 Catalyst characterisation.........................................................................................30
4.2 Fourier Transform Infrared Spectroscopy...............................................................30
4.2.1 Activity measurements ....................................................................................31
4.2.2 Surface intermediates studies (DRIFT) ...........................................................33
4.2.3 Acidity measurements......................................................................................34
4.3 Adsorption studies ..................................................................................................35
5 Experimental Results..................................................................................................... 36
5.1 Catalyst characterisation.........................................................................................36
5.2 Activity studies .......................................................................................................39
 5.2.1 Conversions of reactants over Pt/zeolites ........................................................39
5.2.2 Reaction products formation over Pt/zeolites ..................................................44
5.2.3 Reaction products formation over Pd/Al2O3 ....................................................46
5.3 DRIFT studies.........................................................................................................47
5.3.1 Pt/zeolite catalysts ...........................................................................................47
5.3.2 Pd/Al2O3 ..........................................................................................................50
5.4 TPD studies ............................................................................................................51
5.5 Acidity measurements.............................................................................................54
6 Reaction mechanisms and kinetics ................................................................................ 58
6.1 Proposed reaction mechanisms from literature.......................................................58
6.1.1 PGM/Al2O3-based catalysts.............................................................................58
6.1.2 Pt-loaded zeolite catalysts ...............................................................................59
6.2 Reaction mechanisms .............................................................................................60
6.2.1 Pd/Al2O3-based catalyst...................................................................................60
6.2.2 Pt-loaded zeolites.............................................................................................62
6.3 Kinetic studies ........................................................................................................66
6.3.1 NO reduction by CO over Pd/Al2O3-based catalysts .......................................67
6.3.2 Hydrocarbon-assisted NO reduction................................................................70
7 Discussion ..................................................................................................................... 71
8 Conclusions ................................................................................................................... 74
References
Original papers
 1 Introduction

1.1 General

The abatement of nitrogen oxide (NOX) species, such as NO, NO2, and N2O from the
exhaust gases of automotive as well as stationary sources is a very important aspect of
emission control in terms of having a cleaner environment. The emissions from motor
vehicles were documented as a potential environmental problem more than 60 years ago,
when the first reports of photochemical smog formation by the complex reaction of NOx
with hydrocarbons (HC) were introduced. (Haagen-Smit 1952, Haagen-Smit & Fox 1956,
Acres and Harrison 2004) NOX species are known to cause health problems, including
bronchitis, asthma, and lung cancer, as well as environmental problems such as acid rain
and material corrosion (Acres and Harrison 2004, Topsøe 1997, ACEA 2004, Fritz &
Pitchon 1997). The main sources of NOX emissions are the combustion processes e.g.
burning of fossil fuels in power plants and gasoline in motor vehicles.
Nitrogen oxides are formed from anthropogenic sources via three reactions: oxidation
of nitrogen-containing compounds in fuel (fuel NOX), fixation of atmospheric nitrogen
(thermal NOX), and oxidation of intermediate HCN (prompt NOX). The formation of NOX
depends on the temperature, residence time and oxygen concentration in the combustion
process. Nitrogen oxides in exhaust and flue gases from fossil fuel operating motors,
combustion units and reactors contain mainly NO. (Wojciechowska & Lomnicki 1999,
König et al. 2004, Topsøe 1997)
Nitric oxide (NO) is reported to be thermodynamically unstable. The decomposition
energy of NO is ΔGf0 = -86 kJ/mol. Unfortunately, the decomposition reaction of NO is
inhibited by the high activation energy of 365 kJ/mol. Due to this energy barrier a
catalyst is required to decrease the activation energy. (Fritz & Pitchon 1997, Glick et al.
1957)
Automotive emissions have been regulated since the early 1970s. The legislation
started in the United States by the US Clean Air Act of 1970, which allows for the
controlling of emissions of nitrogen oxides, unburned hydrocarbons and carbon
monoxide (CO). The first catalytic converters able to achieve the emission limits were
installed on cars for the model year 1975. (Acres & Harrison 2004) Over the decades the
 18
legislation has become more demanding in the European Union (EU) and by national
governments as well e.g. in USA, Japan and India. (Heck & Farrauto 1997, Acres &
Harrison 2004, Burch 2004, EU 1970, EU 1998) The Euro emission standards stated by
the EU for automotive exhaust gas emissions were set in action for the first time in 1992
(Euro 1). The most recent emission standard, Euro 4, came into force in January 2005.
Euro emission standards regulate the releases of pollutants of NOx (NO and NO2),
hydrocarbons (HC), and CO as well as particulates. Nitrous oxide (N2O) is not, however,
regulated by Euro emission standards.
The European Commission (EC) adopted the proposal for a new emission standard
(Euro 5) in December 2005. The circulation of the proposal for comments is going on in
the European Parliament and Council. The new regulation is expected to enter into force
at the earliest in mid-2008, and at the latest in 2010. The Euro 5 standard will cut both
NOX and HC emissions by 25 % from gasoline driven cars. The standard also contains
particulate regulation of 0.005 g/km, which will be applicable only to vehicles using lean
burn direct inject (DI) engines. For gasoline driven engines the Euro emission standards
have been tightened as shown in Table 1 (Dieselnet_EU 2005, ACEA 2004, Burch 2004,
EU 2005).

Table 1. EU emission standards for gasoline passenger cars (g/km) (Dieselnet_EU 2005,
ACEA 2004, Burch 2004, EU 2005).
Tier Date CO HC HC + NOx NOx
Euro 1 1992.07 2.72 - 0.97 -
Euro 2 1996.01 2.2 - 0.5 -
Euro 3 2000.01 2.30 0.20 - 0.15
Euro 4 2005.01 1.0 0.10 - 0.08
Euro 5 (EC 12/2005) mid-2008 - 2010 1.0 0.075 - 0.06

During the 1990s, several countries all over the world enacted national laws and emission
standards, mostly based on Euro standards. Figure 1 presents the current and subsequent
stage of the automotive exhaust gas emission standards for NOX, unburned hydrocarbons,
and CO in the EU, USA Federal, and Japan. The regulations of particulate emissions are
also set for diesel vehicles. The emission values of the USA Federal standard have been
changed from g mil-1 to g km-1, and hydrocarbon values do not include methane, i.e. non-
methane hydrocarbons (NMHC), so the values in the table are comparable. The USA/Tier
2 bin 5 -values are the “average” values, which are also equivalent to the values in the
California LEV II standard. (Dieselnet_USA 2004, EPA 2002, Hybrid Cars 2005) As can
be seen in Figure 1, the most demanding standard for the NOX emissions is the USA/Tier
2, which has been phased in the beginning of 2004 and will come fully into force by
2007. In 2005, 50 per cent of new passenger cars must fulfil the Tier 2 regulations. (EPA
1999)
 19
3,50
NOx CO HC
3,00 0,19
0,06
2,50
Emission [g/km]

2,00
2,63
1,50
0,10 0,08 2,63
0,12
1,00 0,02
1,00 1,00 0,63
0,50 0,63
0,08 0,06 0,38 0,04 0,28 0,14
0,00

2
V

r oV

5
r oI

200

200
i er

i er
/E u
/E u

A /T

A /T

an

an
EU
EU

US

US

Ja p

Ja p
Fig. 1. Current and subsequent stage of the emission standards in the EU, USA Federal, and
Japan (Dieselnet_USA 2004, Walsh 1999, EPA 2000, EPA 2002).

The combustion and operation conditions in engines have been further developed to be
leaner, i.e. oxygen rich, to decrease fuel consumption. As a result, the traditional three-
way catalysts (TWC) are no longer effective in reducing NOX. To meet the automotive
emission standards, engines and system control also have to be developed. The
combination system with oxygen sensors, on-board diagnostics (OBD), and a catalytic
converter is required to diminish the emissions at the requisite levels. Provisions for the
use of these applications are proposed in the EU Commission Draft for the new emission
directive. All manufacturers should always provide the OBD-related information to the
manufactures and/or repairers of all components, diagnostic tools or test equipment. (EU
2005, Dieselnet_EU 2005) The stringent environmental legislation and regulations have
also forced petroleum refiners to produce cleaner fuels with lower levels of e.g. sulphur
and aromatics (Dai 1995).

1.2 Selective catalytic reduction (SCR)

For several years, the reduction of NOX in lean conditions and at low temperatures has
been the object of researchers’ great interest because the majority of the harmful
emissions are formed instantly after the starting of the engine (ignition). The combustion
and operation conditions in engines have been further developed to be leaner i.e. oxygen
rich. As a result, the traditional three-way catalysts (TWC) are no longer as effective in
the selective catalytic reduction (SCR) of NOX. This is the main reason for developing
new catalysts and more efficient NOX abatement techniques. (Sirilumpen et al. 1999,
Ingelsten et al. 2004)
Nitrogen oxides can be reduced by using hydrocarbons, ammonia or urea as reductants
in SCR. The injection of unburned fuel or other reductants makes the conditions in the
 20
converter less lean, thereby improving the efficiency of NOX reduction. Selective
catalytic reduction of NOX by hydrocarbons (HC-SCR) has been studied extensively over
numerous metal oxide and zeolite-based precious metal (Pt, Pd, Ir) and base metal (Cu,
Fe, Co) catalysts. (Cho & Yie 1996, Denton et al. 2001, Gerlach et al. 1999a & 1999b,
Hadjiivanov et al. 1999, Ingelsten et al. 2004, Iojoiu et al. 2004, Machida & Watanabe
2004, Maisuls et al. 2003, Shin et al. 1995, Xin et al. 1997a & 1997b) Zeolites have been
studied as adsorption and catalytic materials for emission mitigation from exhaust gases
(Traa et al. 1999, Delahay & Coq 2002, Wojciechowska & Lomnicki 1999).
Pt-containing zeolite materials such as Pt/ZSM-5 (e.g. Burch & Scire 1994, Cho and
Yie 1996, Deeba et al. 1999, Guo et al. 1995, Iwamoto et al. 1994, Keiski et al. 1996,
Obuchi et al. 1998, Shin et al. 1995, Takami et al. 1997, Xin et al. 1997a), Pt/Beta (e.g.
García-Cortéz et al. 2003a & 2003b, Satsuma et al. 2003), Pt/Y (e.g. Amiridis et al. 1997,
Satsuma et al. 2003, Pérez-Ramirez et al. 2001), Pt/FER (e.g. Martens et al. 2001), as
well as Co-Pt/HY (Maisuls et al. 2003) and Pt-transition metal mordenites (Sakamoto et
al. 1997) have been investigated for NOX reduction by hydrocarbons. Platinum-loaded
zeolite catalysts have been found to be effective in the reduction of NOX and at the same
time in the oxidation of hydrocarbons and CO. Pt-zeolite catalysts might be a solution for
the HC-SCR and the oxidation reactions in lean conditions and at low temperatures. To
understand the mechanisms and furthermore the kinetics of the SCR reactions of NOX
there is a need to investigate the surface species and intermediates formed under the
reaction conditions as well as the gas-phase by-products at the catalytic converter outlet.

1.3 Scope and aims of the research

This thesis work is a part of a larger research project, ‘FT-IR studies and kinetic
modelling of catalytic NO-CO-O2 and NO-hydrocarbon-O2 reactions’ carried out in the
Laboratory of Mass and Heat Transfer Process Engineering at the University of Oulu.
The goal of this thesis is to improve the present-day understanding of the reactions
occurring on the surfaces of noble metal catalysts supported on zeolite carriers and to find
correlations between the results obtained by different experimental methods, i.e. in situ
DRIFT, activity, acidity, physisorption, chemisorption, TPD and TEM/EDS studies. An
extensive analysis of present-day literature was used to support the experimental
observations when deriving the reaction mechanism for HC-SCR of NOX. The scope of
this thesis was to gain new knowledge on the selective catalytic reduction of NOX by
propene. The knowledge of the reaction mechanisms and kinetics form the basis for the
development of SCR catalysts and reactors and thus the reaction mechanisms and
reaction intermediates and products have been studied in this work.
The main goal of this work was to derive the plausible reaction mechanisms for NO
reduction by hydrocarbons with propene in particular being the reductant. The platinum-
loaded zeolites have been studied and the formation of intermediates on the catalysts
surfaces has been detected. Pd/Al2O3-based catalysts have been used as a reference
material. Based on the infrared (IR) technique, the catalytic activity and performance of
the catalysts have been investigated and the mechanism of NO reduction in lean
conditions and at low temperatures has been derived. The reaction mechanisms can be
 21
determined via the combined analysis of gaseous products and the identification of the
adsorbed surface species formed during the reactions, and likewise the kinetic equations
can be further derived for the C3H6-SCR of NOX. The kinetic analysis can be utilised in
the reactor design. Studies were carried out by gas-IR and by in situ Diffuse Reflectance
Infrared Fourier Transform Spectroscopy, DRIFTS.
The other main focus was to study the use of the infrared technique, in surface species
identification and activity experiments as well as in acidity measurements, and to study
the applicability of IR and DRIFT techniques as an engineering tool for mechanistic
studies. Temperature Programmed Desorption (TPD) is used to investigate the adsorption
and desorption performances of the catalysts as a function of temperature.
The study has been carried out in collaboration with Ecocat Oy (formerly Kemira
Metalkat Oy), which provided the zeolites and other catalysts’ materials studied. The
experiments were carried out partly in Ecocat Oy’s (DRIFT studies) laboratory and partly
in the Department of Process and Environmental Engineering at the University of Oulu.
This work is comprised of a short overview of the relevant literature, the experimental
part, results, and discussion. Chapter 2 offers a brief review of the recent literature of the
reduction of NOX by hydrocarbons in lean conditions over zeolite and alumina-based
precious metal loaded catalysts. The catalysts studied are introduced in Chapter 3, and the
experimental set-ups and procedures are presented in Chapter 4. In Chapter 5 the
experimental results of the characterisation, activity and surface studies of the catalysts
are presented. The mechanistic models introduced in the recent literature and the derived
mechanistic models based on the observations are reported in Chapter 6. The results and
observations are discussed in Chapter 7. The conclusions of the study are presented in
Chapter 8.
 2 Lean gasoline and diesel conditions
Diesel and lean burn engines have oxygen rich conditions in the burning chambers
(cylinders). In the excess oxygen the air/fuel (A/F) ratio of the mixture is clearly above
the stoichiometric value of 14.7, and can be over 24. Excess oxygen in the exhaust gas
makes traditional three-way catalysts inefficient in reducing harmful NO-containing
exhaust gas emissions. (Kašpar et al. 2003, Burch 2004) The majority of the reductants
are combusted by the excess oxygen. Thus, the selective oxidation of propene with NO is
limited by the competing oxidation with O2 (Ioan et al. 2005).
Figure 2 presents the component removal efficiency of NO, CO, and hydrocarbons as
a function of the air/fuel (A/F) ratio by traditional TWCs (Heck & Farrauto 2001).

Fig. 2. Conversions of hydrocarbons, CO, and NO by three-way catalysts (Reprinted from

Appl. Catal. A 221, Heck & Farrauto, 2001 with the permission of Elsevier).
 23
Typical exhaust gas compositions resulting from incomplete combustion in gasoline and
diesel engines are presented in Table 2. HC, CO, and NOX are found to be the major
pollutants. Unburned, partially oxidised HCs and CO are due the incomplete oxidation of
the reaction gases, and NOX are formed from the nitrogen in air at high engine
temperatures. The λ-values of gasoline, lean gasoline and diesel engines are 1, 1.16, and
1.26, respectively. (Heck & Farrauto 2001, Gabrielsson 2004, Skoglundh & Fridell 2004,
Kašpar et al. 2003).

Table 2. Typical exhaust gas compositions of gasoline and diesel engines (Heck &
Farrauto 2001, Gabrielsson 2004, Roduit et al. 1998, Kašpar et al. 2003, Tabata et al.
1995).
NOX HC CO H2 O2 CO2 H2O SO2 N2
(ppm) (ppm) (ppm) (ppm) (%) (%) (%) (ppm) (%)
Gasoline 900 350 5000 1700 0.5 10 10 15-60 bal.
Lean 1200 1300 a 1300 n.i. 4-12 11 12 20 bal.
Diesel 1135 30 490 n.i. 10.5 7.1 4-5 30 bal.
Diesel 50b 650 330 195 n.i. 14.8 4.3 5 78 bal.
a
calculated as C1, b 50% loading, n.i. not indicated.

The removal of undesired and harmful pollutants from automotive exhaust gases has been
regulated for decades. The catalytic converters used are mainly TWCs. TWC converters
have been developed to operate at the stoichiometric air/fuel-ratio. Lean conditions make
the removal of nitrogen oxides, NO and N2O, more difficult due to the competing
reactions and the lack of reductants (CO and HCs) in the exhaust gas mixture.

2.1 Hydrocarbon-assisted reduction of NOX

The hydrocarbon-assisted selective catalytic reduction (HC-SCR) of NOX has been

studied widely over numerous catalytic materials such as metal oxides and zeolites.
Precious metals (Pt, Pd, Rh, Ir) and base metals (Cu, Fe, Co, Ag, Ni, Ga, Ce, Mn) loaded
on various zeolitic supports have been studied in oxygen rich conditions. The NO
reduction is proposed to go via decomposition or via formation of nitrogen containing
organic species, and further the reactions between these intermediates and NO take place.
(Traa et al. 1999, Brosius & Martens 2004, Obuchi et al. 1998, Xin et al. 1997a, Gerlach
et al. 1999a, Shen & Kawi 2003, Amiridis et al. 1997, Burch & Scire 1994b, Iwamoto et
al. 1994, Petunchi & Hall 1994, Wang et al. 2003).
PGM-loaded oxide-based (e.g. γ-Al2O3, SiO2, TiO2, ZrO2) catalysts have been studied
in the HC-SCR of NOX in recent decades and they have been found to be active catalysts
for the reduction of NOX (Bamwenda et al. 1995, Burch & Watling 1997, Nikolopoulos et
al. 1999).
Zeolite-supported base and precious metal catalysts have been studied in the removal
of nitrogen oxides by hydrocarbons since 1982, when Iwamoto indicated the Cu-ZSM-5
catalyst having activity in NOX reduction. The drawback for the first Cu-based zeolite
 24
catalysts was the activity decrease in the presence of water or sulphur. (Wojciechowska &
Lomnicki 1999)
Several zeolite catalysts (e.g. ZSM-5, zeolite Beta, Ferrierite, Mordenite, and
faujasites) have been studied to find a possible reaction mechanism for the NOX reduction
by hydrocarbons, e.g. methane (Ciambelli et al. 2001, Dĕdeček et al. 2002, Mihaylov et
al. 2004), ethane, ethene (Li & Armor 1994, Burch & Scire 1994b, Iwamoto et al. 1994,
Cho et al. 1995, Cho & Yie 1996), propene, propane (Poignant et al. 2001, Acke &
Skoglundh 1999, Wichterlová 2004, Corma et al. 1997, Papers I-III) and higher
hydrocarbons (Petunchi & Hall 1994, Martens et al. 2001), as well as in simulated diesel
engine exhaust gases (Iwamoto et al. 1994, Wögerbauer et al. 2001, Pontikakis et al.
2001, Ciambelli et al. 2001, Guo et al. 1995). Recently the use of natural gas as a fuel for
automotive engines has raised the level of interest in reducing NOX from the exhaust
gases of natural gas engines. (Ciambelli et al. 2001)
Hydrocarbon-assisted SCR of NO has also been studied with dual pore zeolite
catalysts (Brosius & Martens 2004, Holma et al. 2004) as well as with other metal cation
besides Pt e.g. Co, Mg, La, Ce, In, Ti, or Au (Maisuls et al. 2003, Terada et al. 1997,
Nakatsuji et al. 1995, Traa et al. 1999). Studies have also been carried out with catalysts
which contain metal oxides such as aluminium, cerium and zirconium oxides besides
zeolite materials (Tanabe et al. 2002, Krishna et al. 2002, Kamijo et al. 2001).
Platinum-loaded catalysts have been found to be effective in the abatement of NOX
and at the same time in the oxidation of hydrocarbons (Xin et al. 1997a, Shen & Kawi
2003, Deeba et al. 1999). Platinum-loaded zeolites have been studied in lean exhaust gas
conditions, and they have been found to have good activity in the reduction of NOX.
Moreover, the lower light-off temperature and minor effect of the presence of water in the
case of NOx reduction are reported with Pt-loaded zeolites when compared to Cu-ZSM-5
(Guo et al. 1995). Pt-loaded catalysts are also reported to be more resistant to sulphur
poisoning by SO2 than other catalysts. Pt/ZSM-5 is reported to have good durability
under real exhaust gas conditions. (Gilot et al. 1997, Xin et al. 1997a, Iwamoto et al.
1994, Burch & Watling 1998)
The assumption has been made that Pt-zeolite catalysts might be one possible solution
for the HC-SCR of NOX and the oxidation of HC and CO in lean conditions at low
temperatures. To understand the mechanisms and furthermore to derive the kinetics of the
SCR reactions there is a need to investigate the surface species formed under the reaction
conditions as well as the by-products in the gas phase at the reactor outlet.
The Pt loadings of zeolite catalysts are reported to be generally between 0.05 and 2.4
wt-%, although higher Pt-loaded catalysts, such 7.2 wt-% Pt/ZSM-5, have also been
studied (Burch & Scire 1994, Machida & Watanabe 2004, Xin et al. 1997a & 1997b, Cho
& Yie 1996, Obuchi et al. 1998). Typical loading of the PGM metals has been reported to
be around 1 wt-%, while with the base metals (e.g. Cu, Fe, Co) the metal loading is
reported to be higher. In addition, some studies of propene-assisted SCR of NOX have
been carried out with rather high base metal loadings, e.g. 14 wt-% for Co/Ferrierite
(Ciambelli et al. 2001) or 5.4 wt-% for Cu-ZSM-5 by Amiridis et al. (1997).
The reaction inlet gas generally contained components in the following
concentrations: NO 250-2000 ppm, C3H6 100-2000 ppm, O2 2.5-10%, and H2O 0-10%
(e.g. Acke & Skoglundh 1999, Chen et al. 2004, Giroir-Fendler et al. 2001). In some
 25
studies, SO2 has also been introduced into the inlet gas of the reactor (e.g. Deeba et al.
1999).
The catalytic properties of the zeolite materials are strongly affected by the structural
and acidic properties of the zeolite. The aluminium concentration in the framework or
extraframework also has an influence on the catalytic properties. Acid zeolites are
reported to be effective HC-SCR catalysts when the inlet gases are dry. Zeolites acid sites
are also reported to be the active sites for the hydrocarbon cracking process. (Brosius &
Martens 2004, Corma 1995, Martin et al. 1991) The material acidity is defined relative to
the base used in acid-base interaction. Two types of acidity are found: Brønsted and
Lewis acidity. Many different reactions are catalysed by the acid sites of the material.
With IR spectroscopy the acidity of the materials can be determined and it has been found
to be a very powerful technique allowing the determination of the hydroxyl groups
directly. To measure the acidity of solid catalysts many different probe molecules such as
pyridine, quinoline, diazines, NH3 and CO have been used. The most commonly used
probes are pyridine and NH3 because of their stability and rather easy determination of
Brønsted and Lewis sites by IR spectroscopy. (Corma 1995, Bludau et al. 1998, Zheng et
al. 2004)
The acidic sites can be observed in the 3600-3200 cm-1 region (Si-OH groups), around
3730 cm-1 (terminal silanol groups) and at 1650-1440 cm-1 (probe molecule adsorption).
Brønsted OH on Al can be detected at around 3610 cm-1. (Janin et al. 1991, Parker et al.
1993)
Pyridine is rather bulky, and it has a kinetic diameter of about 0.6 nm. In the case of
zeolites and zeolite-like materials, such as large-pore zeolites (faujasites and mordenites)
as well as medium pore materials (ZSM-5, ZSM-11), pyridine is a suitable molecule for
probing acidic properties. According to Bludau et al. (1998) almost nothing is yet known
about the transport behaviour of pyridine in zeolites’ porous structure. Pyridine can be
adsorbed on the surface in coordinated (Lewis sites) and protonated (Brønsted sites)
forms. The adsorbed pyridine on the Brønsted (PyB) and Lewis (PyL) sites can be
detected at the wavenumbers of 1632 and 1540 cm-1 (PyB), 1490 cm-1 (both PyL and
PyB) and 1620 and 1450 cm-1 (PyL). (Maache et al. 1993, Bludau et al. 1998)

2.2 Abatement of NOX by other reductants

Other reducing components besides HC, such as CO, urea, and ammonia can be used as
reductants for the SCR reactions. Hydrogen is also being studied for the non-selective
reduction of NOX. Small molecules present in the real exhaust gas composition, such as
hydrogen and CO, have been studied as reductants over catalytic materials to understand
the reaction mechanism. (Yokota et al. 1997, Burch & Scire 1994a) In real systems the
hydrocarbon (fuel) or urea injections have been taken into consideration and some
applications have been introduced. (e.g. Gabrielsson 2004)
Yokota et al. (1997) have studied the removal of NO with hydrogen in the presence of
excess oxygen over Pt/mordenite catalysts. The NO conversion was reported to reach the
efficiency of over 80% at low temperatures. They have also suggested that the rate
determining step could be the same in NOX removal with hydrogen and propene in the
 26
presence of excess O2 over Pt-loaded catalysts. (Yokota et al. 1997) Burch & Scire
(1994a) have examined PGM- and Cu-loaded as well as H-ZSM-5 zeolite catalysts in NO
reduction by H2 in the absence of O2. They found out that the PGM-loaded catalysts are
very active (complete NO conversions) at low temperatures and the activity order is as
follows Pt > Rh > Co loaded ZSM-5. The conversions of NO were, however, lower over
Cu- (XNO=90%) and H-ZSM-5 (XNO=25%) catalysts. (Burch & Scire 1994a)
Carbon monoxide is one of the main components present in exhaust gas, and one of
the most important reactions is the NO reduction by CO (Pârvulescu et al. 1998). CO
adsorption has been studied and the CO-SCR experiments have been carried out over the
Pd-loaded TWC and metal substrated zeolite catalysts (Paper V, Keiski et al. 1995, Kolli
et al. 2005).
Both urea and ammonia can be used as reductants in large scale applications like
lorries and busses (Dieselnet_USA 2004, Gabrielsson 2004). The urea or ammonia
addition needs an extra container and, when utilising urea, refuelling has to be provided
by gasoline stations, for instance. The urea-assisted SCR over zeolites has not been
reported widely. Sjövall et al. (2006), Xu et al. (2002) and Sullivan et al. (1995) have
reported the performance and activity of Cu-loaded zeolite catalysts for ammonia and
urea-SCR reactions. In a zeolite catalyst, the large surface area provides a good ammonia
storage capacity. In our studies, the H-, Cu-, and Fe-zeolite-based catalysts were studied
in the ammonia-SCR of NOX with excess oxygen. The results indicate that the best NOX
conversions were achieved over the Fe-loaded Beta and ZSM-5 as well as Cu-loaded
Ferrierite and Mordenite catalysts. (Rahkamaa-Tolonen et al. 2005)
 3 Catalyst materials
Pt-loaded ZSM-5, Beta, Y, and Ferrierite zeolites were studied in NO abatement in lean
conditions by propene. The zeolite catalysts were powders and the Pt loading was 1 wt-%
in the zeolite catalysts, except for Ferrierite (0.8 wt-% Pt). Platinum was inserted into the
zeolite material by the wet impregnation procedure (Keiski et al. 1996).
A palladium-loaded Al2O3-based catalyst was also studied in the reduction of NO by
CO and propene. Pd-loading was 1 and 3 wt-% on the Al2O3-based support. The porous
catalytic material was mounted on a thin (50 µm) flat metal foil.

3.1 Zeolite catalysts

3.1.1 General

In 1756, Swedish mineralogist and nobleman, baron Axel Cronstedt (1722-1765), heated
an unknown mineral and observed water boiling out. He named the new mineral zeolite
from the Greek words: “zeo” and “lithos” meaning boiling stone. (UMIST 2004, Guisnet
& Gilson 2002)
Zeolites are inorganic porous aluminosilicate materials with the general formula of
M2/nO·Al2O3·ySiO2 and having a highly regular structure of pores and cavities. Zeolites
have a three-dimensional, microporous and crystalline structure and they are a
composition of aluminium, silicon and oxygen. Some other alkaline and transition
elements can also be found in the zeolitic structures. Today, numerous natural zeolite
materials have been found and more synthetic zeolites are prepared continuously in
several research laboratories and institutes. (Zeolyst International 1999)
The structures of ZSM-5 (010), Beta (100), Y (111), and Ferrierite (001) zeolites are
presented in Figure 3. Zeolites have a wide range of channels and ring openings. With the
studied zeolites the main channel openings are as follows: ZSM-5 (5.6 x 5.3 Å), Beta (6.6
x 6.7 Å), zeolite Y (7.4 x 7.4 Å), and Ferrierite (4.2 x 5.4 Å). (Baerlocher & McCusker
2000, Armaroli et al. 2001)
 28

Fig. 3. Structures of the a) ZSM-5, b) Beta, c) Y, and d) Ferrierite zeolites (Redrawn from
Baerlocher and McCusker 2000).

ZSM-5 has been studied widely as a catalytic material in several different processes (e.g.
xylene isomerisation) and its structural characters are well defined, having a two-
dimensional structure with 10-ring intersecting channels (Armaroli et al. 2001). Zeolite
Beta has a 12-membered ring and it has been used in the refining and petroleum industry
(Ho et al. 1998). Zeolite Y has been used for several decades as a catalyst for
hydrocarbon reactions (isomerisation, cracking), especially zeolite Y exchanged with rare
earth metals (Ribeiro 1984). Ferrierite is found to be an interesting catalyst for the
isomerisation of linear butenes. Ferrierite contains 10-, 8-, 6- and 5-membered rings in
the structure. (Bordiga et al. 2000, Armaroli et al. 2001)

3.1.2 Pt/zeolite catalyst preparation

The materials studied were powders of parent and Pt-loaded ZSM-5, Beta, Y, and
Ferrierite zeolite powders. The SiO2/Al2O3 ratios of zeolites were 29, 150, 80, and 20,
respectively. Pt-loaded zeolite catalysts were prepared by an aqueous impregnation
procedure. The parent H-from zeolites (zeolite Y as NH4-form) were mixed with a Pt
tetraammine solution and stirred for 10 minutes at 25ºC. The zeolite/water mixture was
centrifuged and the Pt-zeolite was dried at 100°C overnight. After drying, the Pt-zeolites
were calcined in air at 550°C for 1 hour. The Pt loading was verified by atomic
absorption spectroscopy (AAS) analysis. The platinum loadings of the catalysts were
1 wt-% for ZSM-5, Beta, and Y zeolite catalyst, and 0.8 wt-% for Ferrierite. The desired
1 wt-% Pt loading of Ferrierite was not attained due to the preparation method used. The
calculated ion-exchange ratios of the Pt-loaded ZSM-5, Beta, Y, and Ferrierite zeolites
were 9, 47, 25, and 5%, respectively.
 29

3.2 Alumina-based materials

3.2.1 General

Precious metal-loaded Al2O3 has been studied widely in automotive exhaust gas catalysis.
Aluminium oxide (alumina)-based catalysts have been found to be effective in the
reduction of NOX in three-way catalytic converters. Alumina is in the form of γ-Al2O3 in
catalytic support in most cases, because γ-Al2O3 has been found to be one of the most
active porous single oxides and to omit a high surface area. (Shimizu et al. 1999) The
Al2O3 catalysts can also contain other oxides besides alumina, such as Ce, Zr, La, and Ba
oxides, which are used in the catalyst structure as stabilisers and oxygen storage
materials. (Kolli et al. 2005, Paper IV, Paper V)

3.2.2 Pd/Al2O3 catalyst preparation

Al2O3-based Pd-loaded catalysts provided by Ecocat Oy were also investigated. Besides

Al2O3, the support material also contained La2O3 and CexZr1-xO2. The porous catalyst
material was mounted on a thin (~50 µm) flat metal foil, providing a metallic monolith
structure. Palladium was added to the washcoat as an active metal. The palladium loading
was 1 and 3 wt-% on the Al2O3-based support.
 4 Experimental

4.1 Catalyst characterisation

The specific surface areas (based on Brunauer-Teller-Emmett-theory, BET), pore sizes,

and pore volumes (based on Barrett, Joyner and Halenda-theory, BJH) were measured by
N2 adsorption at -196°C. The samples were pre-treated with a heating rate of 10ºC min-1
in vacuum, followed by evacuation at 90ºC for 30 minutes. Samples were then heated
(10ºC min-1) to 350ºC in vacuum and evacuated at 350ºC for 3 hours and cooled to room
temperature. Next the chamber was filled with gaseous nitrogen. Before starting the
experimental procedure, evacuation was performed for 30 minutes at room temperature to
remove gaseous N2. The specific surface area was calculated from the linear part of the
adsorption isotherm. The pore characteristics were determined by the t-plot. Dispersions
of platinum over zeolite supports were detected by a CO chemisorption procedure.
Experiments were carried out by ASAP 2020 from Micromeritics.
The composition and particle morphology of the Pt-loaded zeolite catalysts have been
studied by an Energy-Filtered Transmission Electron Microscopy (EFTEM) Leo 912
Omega equipped with the Energy Dispersive Spectrometer (EDS) detector (Isis). The
sample was diluted in ethanol and stirred. A drop of the mixture was placed on the Cu-
gauze. The sample was then inserted in a high vacuum chamber. The TEM images were
taken with a magnification of 100 000 and the EDS diagram was measured from the
presented area. TEM and EDS were done with the resources of the Institute of Electron
Optics at the University of Oulu.

4.2 Fourier Transform Infrared Spectroscopy

In this study the FTIR (Fourier Transform Infrared) technique was utilised for obtaining
more information about the surface species as well as the reaction products, and to further
extend the knowledge of catalysts activities, adsorption capacities and the formation of
surface intermediates. The FTIR technique has been used in two different ways, gaseous
 31
FTIR measurements as well as measurements of surface adsorbates and intermediates by
the DRIFT method.
The FTIR spectroscopy is a rather old characterisation method, but its use as a tool for
characterisation has increased with the development of computer techniques and
software. One of the inventors was A. A. Michelson, who developed the interferometer.
The FTIR spectrometer consists generally of four pieces: an interferometer, an IR-source,
a detector, and optical mirrors.
DRIFT (Diffuse Reflectance Infrared Fourier Transform) spectroscopy is one of the
FTIR application methods. In the method the IR beam is impinged on the surface of a
material and the beam partially reflects and transmits.
Infrared spectroscopy is based on the measurement of the vibration of molecules.
When IR radiation is passed through a sample of a gaseous molecule, the molecules
absorb certain wavelengths, and these can be measured. The radiation gives energy to the
molecules and the molecules start to vibrate or rotate. The different vibrations, rotations
and their combinations absorb specific wavelengths of the IR radiation. The modes of the
vibration are symmetric and asymmetric stretching and bending as well as rotation.
(TEMET 2000)
The FTIR spectroscopy has been found to be quite a powerful technique to detect the
gaseous components as well as adsorbed surface species. Another advantage of the FTIR
technique is its good accuracy. (Benítez et al. 1994)

4.2.1 Activity measurements

In the activity experiments the powder-like zeolite catalyst samples (0.1 g) mixed with
quartz sand were packed in a tubular quartz reactor (i.d. 9 mm). Quartz sand was used to
keep the gas hourly space velocity (GHSV) constant (around 26 500 h-1) because of the
different weight by volume of the samples. The schematic figure of the catalysts packing
is presented in Figure 4.

Quartz wool

Gas out
Gas in

Quartz sand and Quartz sand Glass tube

sample mix appr. 2 g
l = 2,5 cm

Fig. 4. Schematic figure of packaging the catalyst samples into the tubular reactor.

The catalysts were heated to 500ºC under N2 flow to clean the catalysts’ surface. After
that the catalysts were pre-oxidised by 5% O2/He at 500ºC for 20 minutes and cooled to
room temperature under 5% O2/He flow. The reaction gas mixture (NO 1000 ppm, C3H6
 32
1000 ppm, O2 variable, N2 as carrier gas) was inserted into the reactor with a flow rate of
1000 cm3 min-1. The experiments were carried out as light-off experiments from room
temperature to 550ºC with a heating rate of 10ºC min-1. The temperature was measured
inside the catalyst bed. The reaction gas mixtures in the kinetic experiments are presented
in Table 3.

Table 3. Experimental conditions in activity measurement over the 1 wt-% Pt/zeolite

catalysts.
NO [ppm] C3H6 [ppm] O2 [%]
Exp. 1 800 800 5
Exp. 2 1200 1200 5
Exp. 3 1000 1000 5
Exp. 4 1200 800 5
Exp. 5 800 1200 5

In the case of Al2O3-based catalysts, the monolith catalyst (500 cpsi) was pre-treated by
heating the catalyst to 500°C in a nitrogen flow and after that the catalyst was oxidised at
500°C for 20 minutes. After cooling the reactor to room temperature under oxidizing
conditions the reaction chamber was purged with N2. The reaction gases were inserted
into the reactor at 25°C and the reactor was heated to 500°C at a rate of 10°C min-1. The
inlet gases used in the experiments were 10% NO/N2, 5% C3H6/N2, N2 (99.5%) and dried
air (~21% O2/N2). The total flow rate of the reaction mixture (NO 5000 ppm, C3H6 and
O2 variable, N2 as carrier gas) was 1000 cm3 min-1. During the NO+CO experiments
(Paper V) the inlet gas concentrations were 4000 ppm CO, and 3600 ppm NO in reducing
and 4400 ppm NO in oxidizing atmospheres. In some experiments part of NO was
replaced with O2 to set the inlet gas stream to 2000 ppm NO, and 800 ppm O2 in reducing
and 1200 ppm O2 in oxidizing atmospheres. The heating rate of the catalysts was 20ºC
min-1.
The outlet gas composition was analysed by Gasmet™ FTIR. The laboratory
apparatus consisted of a quartz tube reactor inside an electrically heated furnace, mass
flow controllers (Brooks 5850TR), and magnetic valves for flow selection and insertion.
The mass flow controllers and magnetic valves were regulated by a PC via a LabView
program. The FTIR spectra were recorded for the following components: NO, NO2, N2O,
NH3, CH4, C3H6, CO, CO2, and H2O. In the case of oxygen measurements the analysis of
O2 was done by a paramagnetic oxygen analyser (ABB Advance Optima). The schematic
of the experimental setup for the activity studies is presented in Figure 5.
 33

3
1. Mass flow controllers
2 4 2. Thermocouple
3. Furnace
4. Reactor
5. Temperature controller
6. FT-IR Gasmet™ Analyser
5

Fig. 5. Experimental set-up for the activity measurements.

4.2.2 Surface intermediates studies (DRIFT)

The surface adsorption and intermediates formation over the parent and Pt-loaded zeolite
as well as the Pd/Al2O3-based catalysts were studied by Diffuse Reflectance Infrared
Fourier Transform Spectroscopy technique (DRIFTS). The schematic figure of the
experimental setup is presented in Figure 6.
In situ DRIFTS studies were carried out by a Perkin Elmer 1760X with a heated
reaction chamber (Environmental Chamber, Specac 19930). Catalyst samples were
heated under vacuum to 400°C before oxidation by 5% O2/Ar at 400°C and then cooled
down to room temperature under an oxidizing atmosphere. The vibrations of adsorbed
surface components were detected in the range of 4000–800 cm-1 at a resolution of 4
cm-1. Measurements of propene adsorption in the presence or absence of oxygen and/or
nitric oxide were carried out under a continuous flow.
In the experiments over the zeolite catalysts each spectrum contained 50 scans (in the
case of Y zeolite 100 scans). The spectra were measured at 8 different constant
temperatures between 25 and 400°C. The heating rate between measurements was 10°C
min-1. The reaction gas mixture contained 1000 ppm NO + 1000 ppm C3H6, 1000 ppm
C3H6 + 5% O2 or 1000 ppm C3H6, all balanced by argon. The total flow of the gas
mixture was 150 cm3min-1 in each experiment.
 34
2 Mass spectrometer
PI
Out
3
PI V6
Ar

1 O 2/Ar
IR-beam
PI
NO
V11 V12
CO, HC/Ar, H2/Ar
IR -cham be r

FCs
V4 V9 V8

H C /N 2
H 2 /A r

O 2 /A r
NO
CO

Ar
V10 V7
FIC
TIC
TIC - Temperature Indicator Controller PI(1-3) - Pressure Indicators
FIC - Flow Indicator Controller V - Manual valves
FC - Flow Controllers

Fig. 6. Schematic figure of the experimental set-up for DRIFT studies.

In the case of the Pd/Al2O3-based catalysts the inlet gas mixture contained NO from 5.7
to 8.2% depending on the desired stoichiometric value during the DRIFT measurements.
The NO gas flow rate was kept constant (10 cm3min-1). The spectra were measured at 25,
220, and 260ºC at a resolution of 4 cm-1 by accumulating 20 scans.
In the experiments of NO reduction by CO the inlet gas mixture contained 4000 ppm
CO and 3600 ppm of NO (reducing conditions) or 4400 ppm of NO (oxidizing
conditions). Experiments using O2 were also done by replacing part of NO with O2 as
described in Chapter 4.2.1.

4.2.3 Acidity measurements

The acidity of the zeolitic materials is found to be one of the most important characters
for catalytic performance. The acidic properties of the catalytic materials were studied by
pyridine adsorption. Measurements were done with the DRIFT equipment [Perkin Elmer
1760X with a heated reaction chamber (Environmental Chamber, Specac 19930)]. The
catalyst samples were heated to 400ºC in vacuum with a heating rate of 10ºC min-1 and
evacuated at 400ºC for 60 minutes. After that the sample was cooled to 150ºC and the
background spectrum was measured. Pyridine was adsorbed on the catalyst surface at
150ºC with bubbling argon gas through pyridine at room temperature for 4 minutes. The
first spectrum was measured immediately after the bubbling. The sample was evacuated
for 30 minutes at 150ºC and the second spectrum was measured. The temperature was
then raised to 250ºC and the sample was evacuated for 60 minutes and cooled to 150ºC
for the spectrum measurement. The fourth spectrum was measured after the evacuation of
the sample at 350ºC for 60 minutes and cooling to 150ºC. The resolution was 2 cm-1 and
 35
all the spectra contained 200 scans. The adsorption of pyridine was not done with the
parent and 0.8 wt-% Pt-loaded Ferrierite zeolite catalysts.

4.3 Adsorption studies

The temperature-programmed desorption (TPD) technique can provide useful

information on solid surfaces, interactions of the surface and adsorbed gas molecules, as
well as the thermal stability of surface desorption states. The strength of the bonds
between the adsorbed molecule and the surface can be determined by the temperature at
which the maximum desorption was determined. (Falconer & Schwarz 1983, Lassi 2003)
A photograph of the experimental set-up for the TPD measurements is presented in
Figure 7. The test equipment consisted of a furnace with a chamber of two quartz tubes
inside. The sample (45 mg) was set into the inner tube (i.d. 0.8 cm) between the quartz
wool seals. The analysis was done by an on-line mass spectrometer (Carlo Erba QTMD).
The adsorption gases used were 5% NO/Ar (gas mixture), O2 (99.998%), and C3H6
(99.95%). Helium (99.9996%) was used as a balancing gas.

Fig. 7. Photograph of the TPD experimental set-up.

In the pre-treatment stage, the sample was heated at a linear heating rate (20°C min-1)
under vacuum from room temperature to 450°C, followed by evacuation for 20 minutes
at 450°C. The sample was oxidised (10% O2/He) at 450°C for 10 minutes and then
cooled to room temperature under a flow of 10% O2/He, and then purged by a He flow
(60 cm3min-1) for 15 minutes. After the He purge the mixture of adsorption gases was
inserted for 10 minutes into the reaction chamber at room temperature. The adsorption
gas contained 5% NO/Ar, 5% C3H6/He, or (5% C3H6 + 5% O2)/He gas mixtures. The
TPD measurements were carried out under vacuum from room temperature to 750°C with
a heating rate of 20°C min-1. The masses 16 (O), 18 (H2O), 28 (CO, N2), 30 (NO), 32
(O2), 42 (C3H6), 44 (CO2, N2O), 46 (NO2) were recorded.
 5 Experimental Results

5.1 Catalyst characterisation

The measured specific surface areas (SBET, N2 adsorption), internal surface areas, pore
sizes and volumes of parent and Pt-loaded zeolites as well as the Pt dispersions of Pt-
loaded zeolite catalysts are summarised in Table 4. The measured values are in agreement
with the literature values (e.g. Kinger & Vinek 2001). With the Pt-loaded ZSM-5, Beta, Y,
and Ferrierite zeolite samples the SBET values were measured to be 364, 488, 524, and
295 m2g-1, respectively. The accuracy of the total surface area values was ±3%. The
internal surface areas have been determined by the t-test method. The Pt loading
increased the SBET value of ZSM-5 and Ferrierite, but reduced that of Beta and Y. (Papers
I and II) The average pore volumes of the parent zeolites were 0.13 cm3g-1 (ZSM-5), 0.20
cm3g-1 (Beta), 0.21 cm3g-1 (Y), and 0.17 cm3g-1 (Fer). The pore volumes were observed to
increase with the platinum loading. The platinum dispersion of the Pt-loaded zeolite
catalysts was measured to be around 12%. However, the Pt dispersion of the 0.8 wt-%
Pt/Ferrierite was detected to be over 33%.
For the Al2O3, La2O3 and CexZr1-xO2-containing Pd-based catalyst the surface area was
measured to be around 40 m2g-1. The palladium loadings were 1 or 3 wt-% (Paper IV).
The average pore sizes of the alumina-based support and the palladium dispersion were
not determined.
 37
Table 4. Measured specific surface areas, average pore sizes, pore volumes, and platinum
dispersions of the ZSM-5, Beta, Y, and Ferrierite zeolite-based catalysts studied.
Pt loading Total surface area Internal surface Pore Pore Pt dispersion
(BET) area size volume
[%] [m2g-1] [m2g-1] [nm] [cm3g-1] [%]
ZSM-5 - 347 224 2.62 0.13 -
Beta - 527 296 6.54 0.20 -
Y - 608 482 3.08 0.21 -
Ferrierite - 282 235 3.58 0.17 -
Pt/ZSM-5 1.0 364 221 2.83 0.25 11.6
Pt/Beta 1.0 488 274 7.60 0.92 11.8
Pt/Y 1.0 524 291 3.72 0.47 12.1
Pt/Ferrierite 0.8 295 247 2.74 0.20 33.3

Figure 8 shows the N2 physisorption isotherms of the Pt-loaded zeolite catalysts. In the
case of the parent zeolites, unique shapes of isotherms were measured. As can be seen, all
the studied zeolite materials have the shape of the isotherm of type I. The type I isotherm
is reported to be typical for materials that have a microporous structure. (Gregg & Sing
1982, Webb & Orr 1997, Intriago et al. 2006)
The isotherms in Fig. 8 are used, after certain approximations (e.g. pore shape,
tortuosity), for the calculations of the numerical values presented in Table 4. The pores
may, however, have different structures and they can also be interconnected with one
another. (Webb & Orr 1997)

30

Pt-ZSM-5 ads
Pt-ZSM-5 des
25 Pt-Beta ads
Pt-Beta des
Pt-Y ads
Adsorbed quantity (mmol/g)

Pt-Y des
20 Pt-Fer ads
Pt-Fer des

15

10

0
0,0 0,2 0,4 0,6 0,8 1,0
Relative pressure (p/p°)

Fig. 8. N2 adsorption and desorption isotherms of Pt-loaded ZSM-5, Beta, Y and Ferrierite
zeolites.
 38
In Figure 9 the EFTEM images of Pt-loaded ZSM-5, Pt-Beta, Pt-Y, and Pt-Ferrierite
zeolite catalysts are presented. All images (a-d) are on the same scale (magnification of
100 000). The Pt clusters are found to be of the size of 5-10 nm. In the case of Pt/ZSM-5
some of the Pt clusters are also found to be much bigger than 10 nm. The EFTEM images
indicate that the smallest platinum particles are in Pt-loaded Beta zeolite samples. The
TEM images ensure that very large extra framework Pt particles can also be found
besides platinum in the pores of the zeolite framework.

a) b) c) d)

Fig. 9. TEM images of the Pt clusters on the a) ZSM-5, b) Beta, c) Y, and d) Ferrierite zeolite
surfaces, respectively. Black particles indicate the Pt clusters and the dark grey form are due
to the zeolite support. Magnification: ¯100 000.

Figure 10 presents an example of the EDS spectra from the 1 wt-% Pt-loaded ZSM-5
zeolite. The Cu bands are due to the Cu-gauze of the sample holder. The spectra are taken
from the area as presented in Figure 9a. The bands from platinum can be detected with all
the studied catalysts, which indicates that the black particles are Pt clusters.

Fig. 10. Example of the EDS spectra (1 wt-% Pt-loaded ZSM-5 zeolite catalyst).
 39

5.2 Activity studies

The activity of a catalyst is one of its most important characteristics. Effectiveness in

reducing nitrogen-containing compounds (NOX) and to oxidise unburned hydrocarbons as
well as CO simultaneously is crucial in designing catalysts to meet stringent emission
standards at low temperatures and in lean conditions.
In the laboratory tests the reactor outlet gas composition was measured to contain
mainly nitrous oxide, nitrogen dioxide, carbon monoxide, carbon dioxide and water, in
addition to the inlet reaction gases.

5.2.1 Conversions of reactants over Pt/zeolites

The conversions of NO and propene in the reaction gas mixture of NO+C3H6 balanced by
nitrogen over Pt-loaded zeolite catalysts are presented in Figure 11. The conversions of
NO and propene can be observed to be at their maximum at over 300°C. NO conversion
is detected to be the highest with 0.8 wt-% Pt/Ferrierite zeolite, achieving conversion of
over 99%, while the conversion of NO over the other studied catalysts can be detected to
be around 50%. The light-off temperature of the NO reduction is lowest over the 1 wt-%
Pt/Y (T50 = 339°C) after which comes 0.8 wt-% Pt/Ferrierite (345°C) followed by 1 wt-%
Pt/ZSM-5 (565°C). Over the 1 wt-% Pt/Beta the conversion of NO did not reach the 50%
value. At low temperatures hydrocarbons are adsorbed on the surface and at around
100ºC desorption can be observed (negative conversions). This phenomenon is later
testified by TPD measurements (Figures in Section 5.4).
In the NO+C3H6 mixture, propene is oxidised only by oxygen formed from nitric
oxide. The light-off temperature of propene can be detected to be lowest over the
Pt/ZSM-5 catalyst, which is the only one having the conversion of propene higher than
50%. The rather high conversions with Pt-loaded ZSM-5 and Ferrierite zeolites below
100°C are due to the adsorption of propene on the catalyst’s surface.
 40

120
1 wt-% Pt/ZSM-5 a) a)
1 wt-% Pt/Beta
100 1 wt-% Pt/Y
0.8 wt-% Pt/Fer
NOX Conversion [%]

80 MaxNOX (Z) = 71%

MaxNOX (B) = 48%
60 MaxNOX (Y) = 59%
MaxNOX (F) = 98%
40

20

-20
0 100 200 300 400 500 600
Temperature [°C]

120 b)
b) 1 wt-% Pt/ZSM-5 T50 (Z) = 474°C
1 wt-% Pt/Beta T50 (B) = - - °C
100 1 wt-% Pt/Y T50 (Y) = - - °C
0.8 wt-% Pt/Fer T50 (F) = - - °C
C3H6 Conversion [%]

80

60

40

20

-20
0 100 200 300 400 500 600
Temperature [°C]

Fig. 11. a) NO and b) C3H6 conversions and light-off temperatures of Pt-loaded zeolites with a
reaction gas mixture of 1000 ppm NO, 1000 ppm propene, balanced by N2.
 41

100
a)
a) 1 wt-% Pt/ZSM-5
1 wt-% Pt/Beta
80 1 wt-% Pt/Y
0.8 wt-%Pt/Fer
NOx Conversion [%]

NO
Max X (Z) = 32%
60 NO
Max X (B) = 68%
MaxNOX (Y) = 60%
40 MaxNOX (F) = 41%

20

-20
0 100 200 300 400 500 600
Temperature [°C]

120 b)
b)
100
C3H6 Conversion [%]

80

60
1 wt-% Pt/ZSM-5
40 1 wt-% Pt/Beta
1 wt-% Pt/Y
0.8 wt-% Pt/Fer
20
T50 (Z) = 253°C
T50 (B) = 208 °C
0 T50 (Y) = 198°C
T50 (F) = 227°C
-20
0 100 200 300 400 500 600
Temperature [°C}

Fig. 12. a) NO and b) C3H6 conversions and light-off temperatures of Pt-loaded zeolites with a
reaction gas mixture of 1000 ppm NO, 1000 ppm propene, and 5% oxygen balanced by N2
(Paper II).
 42
Conversions of NO and C3H6, and the maximum NO conversion reached, as well as the
light-off temperatures of propene over the Pt-loaded zeolite catalysts in lean conditions
(excess oxygen), are shown in Figure 12 (Paper II). The negative conversions are
explained by desorption phenomenon as in the experiments without O2 (Figure 11).
As reported (Paper II), NO conversions were observed to increase as a function of
temperature up to 220-270ºC. Over the 1 wt-% Pt/ZSM-5 and 0.8 wt-% Pt/Ferrierite
catalysts the conversion of NO did not exceed 50%, while the highest conversions were
observed over the 1 wt-% Pt-loaded Beta and Pt/Y zeolites. The maximum conversion of
NOx was almost 70% over Pt-Beta and 60% over Pt/Y. NO conversions started to
increase at above 150ºC over all the catalysts except Pt/ZSM-5, over which the reaction
was initiated at 250ºC. The maximum NO conversions were measured just above the
temperature at which propene had reached conversion of higher than 99%. NO
conversion remained quite stable in a wide temperature window and also at temperatures
above 350ºC over the 1 wt-% Pt/ZSM-5 catalyst. The maximum conversions of NO over
the 1 wt-% Pt-loaded ZSM-5, Beta, Y, and Ferrierite zeolites were achieved at 267, 245,
232, and 262ºC, respectively. At temperatures higher than the temperature where the
maximum NO conversion was reached, the observed conversion values started to
decrease rapidly. This can be explained by the oxidation reaction of propene that is
favoured over O2 compared to NO (Peréz-Ramírez et al. 2001, Fritz & Pitchon 1997).
NO conversions in the absence and presence of excess (5%) oxygen are summarised in
Figure 13.

100
1% Pt/ZSM-5
1% Pt/Beta
1% Pt/Y
80
0.8% Pt/FER
1% Pt/ZSM-5, O2
NO Conversion [%]

1% Pt/Beta, O2
60 1% Pt/Y, O2
0.8% Pt/FER, O2

40

20

-20
0 100 200 300 400 500 600
Temperature [°C]

Fig. 13. NO conversions in the absence and presence of excess oxygen over the Pt-loaded
catalysts.
 43
Propene is observed to reach the 50% conversion over all the studied Pt-loaded catalysts
at temperatures from 200 to 253°C. High conversions of propene at low temperatures
(below 100ºC) are caused by propene adsorption on the catalyst surface. The lowest light-
off temperature (T50) of propene (198°C) can be measured over the Pt/Y zeolite catalyst.
The light-off temperatures of Pt-loaded catalysts increased in the following order: Pt/Y ≤
Pt/Beta < Pt/Ferrierite < Pt/ZSM-5. The propene conversion above the light-off
temperature was higher than 99% over all the studied catalysts. In the case of the parent
zeolite materials propene also reached conversions of >99% at temperatures above
450ºC, and the light-off temperatures of propene over the parent ZSM-5, Beta, Y, and
Ferrierite zeolites were 413, 401, 421, and 391ºC, respectively. When comparing these
T50 values to the values of Pt-loaded zeolites, the numerical values of the light-off
temperature can be observed to rise in the order: Pt/Y ≤ Pt/Beta < Pt/Ferrierite
< Pt/ZSM-5. Platinum loading can be detected to have the lowest effect in the case of
ZSM-5 and Ferrierite-based zeolites, but it has the most significant effect on the
reduction of light-off temperature over Y- and Beta-based zeolite catalysts. The smaller
average pore size of Ferrierite and ZSM-5 zeolites can possibly be one reason for the
smaller decrease in the light-off temperature over the Pt-exchanged Ferrierite and ZSM-5
(e.g. pore blocking, availability of active sites). The comparison of the light-off
temperatures between Pt-loaded and parent zeolites is presented in Figure 14.

500
413 421
401 391
Light-off temperature [°C] .

400

300
253 parent
227
208 198 Pt-loaded
200

100

0
ZSM-5 Beta zeol. Y Ferrierite

Fig. 14. Comparison of the light-off temperatures of propene over the parent and Pt-loaded
zeolite catalysts (1000 ppm NO, 1000 ppm C3H6, 5% O2).

In Figure 15 (Paper III) the maximum in NO conversion was measured over ZSM-5 at
477ºC (XNO = 8%) and over Pt/ZSM-5 at 263ºC (XNO = 32%). The Pt loading can be
concluded to significantly increase the conversion of NO even at low temperatures. The
presence of platinum was also detected to decrease the light-off temperature of propene
from 400°C to 240°C.
 44

100
C3H6
80
Conversion (%)

60

40
NO
20

0
0 100 200 300 400 500 600
-20
Temperature (°C)

Fig. 15. Comparison of the conversions of NO and propene over the parent (S and U) and
Pt-loaded ZSM-5 (… and —) zeolite catalysts (Paper III).

5.2.2 Reaction products formation over Pt/zeolites

The formations of desired products (CO2, H2O) as well as by-products (CO, N2O, NO2)
during the activity experiments were detected. The formation of molecular nitrogen
cannot be measured because a homonuclear diatomic species does not have an infrared
adsorption band, and therefore the detection of these compounds is impossible by the
FTIR technique. The maximum concentrations of the by-products formed are collected in
Table 5.

Table 5. Maximum by-product (CO, N2O, and NO2) concentrations measured in the
NO+C3H6+O2 reaction gas mixture on parent and 1 wt-% Pt-loaded ZSM-5, Beta, Y, and
Ferrierite catalysts.
Catalysts CO N2O NO2
ci [ppm] at T [ºC] ci [ppm] at T [ºC] ci [ppm] at T [ºC]
ZSM-5 1080 420 8 ~310 110 410
Beta 1560 463 7 ~460 137 445
Y 1730 484 11 ~530 107 467
Ferrierite 1490 528 9 513 103 504
Pt/ZSM-5 115 253 150 275 207 371
Pt/Beta 33 214 156 244 412 280
Pt/Y 48 202 124 210 410 255
Pt/Ferrierite 43 210 108 243 228 320
 45
The formation of CO2 from propene was detected to be at the maxima at the light-off
temperature of each catalyst. The 1 wt-% Pt/ZSM-5 zeolite seems to produce CO2 just
above the light-off temperature, which is most probably caused by the oxidation of
adsorbed C3H6 species on the catalyst surface. The strongest adsorption of propene at
temperatures below 70ºC was detected over the Pt/ZSM-5 catalyst. With the other
samples studied, the oxidation of the carbon-containing surface species to CO2 was not
detected to be as strong, while more CO2, than can be formed from propene was
measured with all the catalysts after the light-off temperature was reached. The results
correlate well with the results of Furusawa et al. (2002).
Generally only small amounts of partially oxidised hydrocarbons, mainly CO, as well
as nitrogen oxides (NO2 and N2O) were formed around the light-off temperature of
propene over all the Pt-loaded catalysts.
Carbon monoxide (CO) formation was detected with all the samples studied. With Pt-
loaded samples the formation was below 50 ppm at the maximum, except with 1 wt-%
Pt/ZSM-5 zeolite catalyst with which the formation was detected to be around 115 ppm.
The maximum concentration can be measured at the light-off temperature of propene
over all the catalysts. Over the parent zeolite samples the formation of CO was measured
to be more than 30 times higher. The temperatures at which the maximum formation
occurs were also much higher, being above 400°C. The CO concentration on the parent
zeolites were detected to be between 1080 ppm (ZSM-5) at temperatures around 420°C
and 1730 ppm at 484°C (zeolite Y). On the platinum-loaded zeolites the concentration of
CO decreased rapidly at the light-off temperature. (Paper III) In the complex oxidation of
propene over the catalysts studied CO is formed as an intermediate (Table 5). Over the
parent zeolites the oxidation of CO to CO2 is probably very slow and adsorbed CO is
desorbed causing an increase in the CO emissions (Petersson et al. 2005). In the presence
of Pt the oxidation of CO to CO2 is much faster and desorption of CO is thus reduced.
Nitrogen dioxide is observed to be formed at temperatures above the light-off
temperature having maxima of 107 ppm (at 467ºC) over the Y zeolite and 412 ppm (at
280ºC) over the 1 wt-% Pt-Beta. Over the 1 wt-% loaded Beta and Y zeolites the
formation of NO2 are measured to be over 410 ppm, while in the case of the Pt-loaded
ZSM-5 and Ferrierite the formation can be detected to be around 200 ppm. Over the
parent zeolites the formation remained below 150 ppm. NO2 formation is observed to
decrease at temperatures above 300°C because of the equilibrium limitation.
The formation of nitrous oxide over parent ZSM-5, Beta, Y and Ferrierite was detected
to be below 10 ppm. Over the 1 wt-% Pt-loaded zeolite catalysts the maxima are
measured at around the light-off temperatures, being 108 ppm, at the lowest, over Pt-
Ferrierite and the highest (156 ppm) over the 1 wt-% Pt/Beta. Nitrous oxide formation
can be measured at around the light-off temperature of propene over all Pt-loaded
catalysts. The formation decreased rapidly at the light-off temperature and remained
below the 5 ppm level.
Platinum loading can be observed to have a positive impact on the efficiency of a
catalyst in oxidising hydrocarbons. The formation of CO is measured to be less than 10
per cent of the formation with the parent zeolites. The detected phenomenon can be
concluded to be evidence of the hydrocarbon cracking due to the influence of platinum
particles and furthermore the hydrocarbon species (CHx) formed can react much more
efficiently with the surface oxygen or NO species.
 46
On the other hand, NO2 formation rises to twofold in magnitude with all the Pt-loaded
catalysts studied compared to the parent (H-ZSM-5, H-Beta, NH4-Y and H-Ferrierite)
zeolites. According to the literature, the first step in the reduction of NO in the presence
of O2 over the parent zeolites (Y, ZSM-5) is the oxidation of NO into NO2 (e.g. Amiridis
et al. 1996, Schmieg et al. 2004). This can also be seen from our results (Table 5). The
presence of Pt increases the oxidation of NO considerably. Platinum can also be
concluded to have an effect on O2 and NO dissociation. More rapid oxidation of NO and
propene can be observed over zeolites with a platinum loading.

5.2.3 Reaction products formation over Pd/Al2O3

The conversion of NO over the Pd/Al2O3-based catalyst reached over 99% in rich and
stoichiometric conditions, while in lean conditions (excess oxygen or NO present)
conversions up to 80% were obtained in the activity experiments. The high NOx
conversion in lean exhaust gas conditions can be explained by the inlet mixture, when
NO is the only oxidant. Therefore C3H6 reacts totally with NO in the absence of oxygen.
In real exhaust gas the O2/NO ratio is, however, much more than 1.0 (Paper V).
The formation of harmful by-products like ammonia (NH3), carbon monoxide (CO),
and nitrous oxide (N2O) is not desired and therefore the amount of these compounds after
the catalyst should be as low as possible. According to our experiments (Figure 16) those
components were formed but the measured amounts of CO and NH3 are rather small (65-
120 ppm CO, 30-60 ppm NH3) except in rich concentrations (1100 ppm CO, 1700 ppm
NH3). The formation of NH3 and CO started at 200°C and the maxima were observed at
the light-off temperature (~250°C). These by-products were due to incomplete oxidation
of hydrocarbons. NH3 is formed in reactions between hydrocarbons and nitrogen oxides.
It is also possible that on γ-Al2O3 surface intermediates like Al-NCO and H-NCO are
converted to NH3 and CO2. (Radtke et al. 1997, Cowan et al. 1998)
The formation of N2O was observed to start at 200°C and the formation reached the
maximum at around 300°C. The formation of N2O was significantly smaller in rich than
in lean or stoichiometric conditions. Nitrous oxide was expected to be formed in reactions
between cyanides or isocyanates and nitrates or nitrites at the surface. NO can react with
surface nitrogen atoms to N2O. N2O formation can also take place via isocyanate
complexes and NO or NO2. The amount of N2O formation was the highest in lean
conditions and it could be detected in all experiments.
The total oxidation of propene seemed to be quite effective as no evidence of lighter
hydrocarbons was detected. It is possible that in rich conditions, self-poisoning of the
catalyst may also occur and therefore the reduction of NO is lower than in stoichiometric
conditions. (Macleod 2001)
 47

Concentration Concentration
[ppm] [ppm]
6000 120
Nitric oxide NO
° Propene C3H6
5000 NO Nitrogen N2 100
U Nitrous oxide N2O
Water H2O
4000 Carbon monoxide CO 80
Ammonia NH3

3000 60
CO
H2O
2000 40
N2

1000 NH3 20
C3 H6
N2 O
0 0
100 150 200 250 300 350 400 450 500
Temperature [°C]

Fig. 16. An example of the concentrations of reactants and products as a function of

temperature in lean conditions, 5000 ppm NO, 400 ppm C3H6, over 1% Pd/Al2O3. The N2
concentration is a calculated value. (Paper V)

5.3 DRIFT studies

5.3.1 Pt/zeolite catalysts

The DRIFT spectra of the NO+C3H6+O2 reaction gas mixture over the Pt-loaded ZSM-5
zeolite catalyst is presented in Figure 17. The analyses of the DRIFT spectra were based
on the assessment of the obtained experimental bands with the observations reported in
the literature by other researchers.
 48

1460 1414 1190

0.5 1595
3200-2800 1662
1820
400 °C 1935
2280
350
Absorbance [a.u.]

300
250

200
150
100
25

4000 3500 3000 2500 2000 1500 1000

Wavenumber [cm-1]

Fig. 17. DRIFT spectra of adsorbed surface species over 1 wt-% Pt/ZSM-5 as a function of
temperature. Reaction gas mixture: 1000 ppm NO + 1000 ppm C3H6 + 5 vol-% O2. (Paper
III)

The surface species were assigned to CHX species, nitrates and nitrites, carbonates,
organic nitro compounds and partially oxidised hydrocarbons such as acetates and
formates as well as carbon monoxide (Gerlach et al. 1999a, Xin et al. 1997a & 1997b,
Papers I-III).
Over the parent as well as 1 wt-% Pt-loaded ZSM-5, Beta and Ferrierite zeolites
adsorbed propene and fragmented CXHY species were assigned at 3200-2900 cm-1.
Adsorption of propene over the parent and Pt-loaded Y zeolites was almost undetectable.
A band observed at 1507 cm-1 was assigned to the C-H bending vibrations (Gerlach et al.
1999a) and a band at around 1650-1620 cm-1 to the C=C vibrations of propene
(Radziszewski et al. 1996, Hoost et al. 1995a). Linearly bonded C3H6 can also be
detected over ZSM-5 zeolite catalysts at 1470 cm-1. This band was not detectable on other
zeolite surfaces. The adsorption of propene can be detected to be more intensive over the
Pt-loaded samples between temperatures from 100 to 250ºC. Propene was observed to
adsorb on the Pt/Y zeolite at 25ºC, but no adsorption can be detected over the parent Y
zeolite. It is proposed that propene is mainly adsorbed on the Pt-sites. This phenomenon
can be assumed to be the same over all the Pt-loaded zeolite catalysts.
Formation and adsorption of CO can be detected at 1190 cm-1 over the parent and 1
wt-% Pt-loaded ZSM-5 zeolite catalysts. When increasing the temperature, the adsorption
bands increased up to 250ºC. Above that temperature the adsorption bands decreased. The
band detected at 1595 cm-1 was assigned to COO- or CO2- of adsorbed acetates or
formates (Xin et al. 1997a). This band was found to be much weaker with the reaction
gas mixture of NO+C3H6+O2 than with C3H6+O2. The Pt loading had an effect on water
formation over zeolite catalysts. Over all the Pt-loaded catalysts studied, except Pt/Y
 49
zeolite, a broad band due to adsorbed H2O at the OH-region at 3500-3100 cm-1 was
observed. This can not be detected on the parent zeolite catalysts. (Papers I-II)
A broad band at around 1850 cm-1 was assumed to be due to NO adsorption (Iojoiu et
al. 2004). Nitrates and nitrites formed via the reaction between the adsorbed NO and
surface oxygen species (O2-) caused multiple bands below 1900 cm-1. Over the 1 wt-%
Pt/ZSM-5 zeolite the band at 1696 cm-1 due to adsorbed NO2 was observed. The band at
1935 cm-1 can be assigned to the adsorbed NO on the Pt-site based on the observations by
Xin et al. (1997b). The broad band at around 1970-1920 cm-1 and a band at 1820 cm-1
were assumed to be due to NO and (NO)2 species adsorbed on Pt and partially oxidised Pt
sites. (Xin et al. 1997b, Tabata et al. 1998, Hadjiivanov et al. 1999, Paper II)
Comparising our data with the studies made by Gerlach et al. (1999a, 1999b) the
bands detected at 1460 and 1414 cm-1 were proposed to be caused by the propenal oxime
intermediate formed in the reaction between NO and propene. Satsuma et al. (2003) have
proposed the band at around 1450 cm-1 on Pt/ZSM-5 to be due to the NH4+ ion adsorbed
on the Brønsted acid site. Organic nitro or nitrite species assigned such as C3H7-ONO,
e.g. by Iojoiu et al. (2004), can be observed at 1662 cm-1 on ZSM-5 and 1 wt-%
Pt/ZSM-5.
Figure 18 shows the adsorption of propene with oxygen over the studied catalysts at
100ºC. The adsorption of propene can be seen to be the most significant over the parent
and 1 wt-% Pt/ZSM-5 as well as 1 wt-% Pt/Beta. The parent Beta and 0.8 wt-%
Pt/Ferrierite zeolites showed a weaker adsorption of propene than the catalysts mentioned
previously. Over the rest of the studied catalysts propene adsorption was determined to be
almost negligible at 100ºC.
The formation of intermediate species can be observed to be the strongest over the
parent and Pt-loaded ZSM-5 zeolites, however, over the 1 wt-% Pt/Beta oxidised HC
species such as carbonates can be detected at around 1530 cm-1. (Hoost et al. 1995a)
 50

0.5 a.u.

2980

1578

1105
2912

923
Pt-Ferrierite

Ferrierite
Adsorbance [a.u.]

Pt-Y zeolite

N o i s e
Y zeolite

1534
2107
Pt-Beta
2935
2862
2958

Beta
3452

2107

1556
Pt-ZSM-5

1470

1190

957
1957
1854
ZSM-5
2933
2860
3700

2361

4000 3500 3000 2500 2000 1500 1000

Wavenumber [cm-1]

Fig. 18. DRIFT spectra of adsorbed surface species over parent and Pt-loaded zeolites at
100ºC. Reaction gas mixture: 1000 ppm C3H6 + 5 vol-% O2. (Paper I)

5.3.2 Pd/Al2O3

Simultaneous adsorption of NO + C3H6 (+O2), and NO + O2 over the 1% Pd-catalyst at

260°C is presented in Figure 19. Formation of isocyanates can be seen at 2253-2233 cm-1
when the gas mixture contains propene. This finding is in agreement with the studies
reported in the literature (e.g. Bamwenda et al. 1995, Radtke et al. 1997). The amount of
isocyanate species formed is small in stoichiometric conditions compared to fuel rich
conditions.
The adsorption bands from partially oxidised hydrocarbons like formates (1393 and
1379 cm-1) as well as acetates (1567 and 1463 cm-1) are detected. These surface
intermediate species are most probably interacting with aluminium (Ermini et al. 2000,
Shimizu et al. 1998, Shimizu et al. 1999). In the fuel rich conditions strong adsorption
bands caused by formates are found on the surface. The intensity of these bands decreases
when the experiment is done in lean conditions. Formate species were observed to be
more visible in the adsorption spectra when the reaction between NO and propene was
done without the addition of oxygen (Figure 19).
In the beginning of the experiment the formation of nitrates and nitrites was strong in
the region from 1300 to 1250 cm-1. These bands disappeared in rich conditions at 260°C,
 51
but at 260ºC these bands can still be observed in lean and stoichiometric conditions. It
seems quite evident that NO and oxygen react to nitrate species at the surface when the
amount of reductant is very small or absent.
Hoost et al. (1995b) proposed that a band at around 1630 cm-1 is probably caused due
to NO on palladium when the reaction gas contains propene as a reductant. In the NO +
O2 reaction gas mixture, the bent NO band is also present. The observed band at
1658 cm-1 can be assigned to an organic nitrite compound (R-ONO) (Meunier et al. 1999,
Tanaka et al. 1994). According to the literature linear NO adsorption, Pd-N=O (ca.
1750 cm-1), on Pd over an oxidised catalyst is not evident. (Hoost et al. 1995a) Our
experimental results are in agreement with the literature. In reducing conditions (NO +
C3H6) it is probably adsorbed COO- that causes the band observed at 1600 cm-1.
In rich reaction conditions the formation of ammonia and carbon monoxide was
significant. It could be due to the reaction between isocyanates and cyanides and water to
ammonia and CO or CO2.

COO- and NO3-

T = 260 °C
1593

NO3-
1567

NO2 and NO3-

bent NO

1252
1301
1630

0.25 a.u.

NO -NO2
gas
Adsorbance [a.u.]

1658
1725
2360

1875

NO + O2 acet.
form.
1453
1463

1379
1393

-NCO -CN
2232
2253

lean
2163

with oxygen

stoich.

rich

2600 2400 2200 2000 1800 1600 1400 1200 1000

Wavenumber [cm-1]

Fig. 19. The spectra of NO + C3H6 reaction on 1 wt-% Pd/Al2O3 catalysts at 260°C in fuel
rich, stoichiometric, and lean conditions with excess O2 conditions. The NO+O2 spectrum is
also shown. (Paper V)

5.4 TPD studies

Temperature Programmed Desorption (TPD) measurements have been carried out to

determine the adsorption of propene and NO over parent and Pt-loaded zeolite catalysts.
The adsorption of propene was studied with propene and a mixture of propene plus
oxygen. The adsorption of NO was studied as well. The simultaneous adsorption of a
 52
mixture of propene, NO and oxygen was not tested because of the limitations of the mass
spectrometer, and due to the many similar masses of species containing C and N atoms.
Figure 20 shows the results of the NO-TPD studies (Paper I). The desorption bands of
NO can be detected at around 70ºC with the parent zeolite materials, while in the case of
the Pt-loaded zeolite catalysts the second band at around 120ºC on Pt/ZSM-5, at around
140ºC on Pt/Beta, and at 350°C on Pt/Y zeolite can be observed. This is concluded to
indicate that at least two types of NO adsorption sites are available at the catalyst surface.
With Ferrierite the second band can not be observed. The only desorption band can be
found at 70ºC on both parent and Pt-loaded Ferrierite.

1,6e-4 ZSM-5 2e-5 Y

Desorption rate [a.u]

Beta Fer
Y Pt-Y
2e-5
Fer Pt-Fer
Pt-ZSM-5
Desorption rate [a.u.]

1,2e-4 1e-5
Pt-Beta
Pt-Y
Pt-Fer 5e-6

8,0e-5 0
0 100 200 300 400 500 600

4,0e-5

0,0
0 100 200 300 400 500 600
Temperature [°C]

Fig. 20. TPD study of NO desorption over parent and Pt-loaded zeolites. In the interior graph
desorption over the parent and Pt-loaded Y and Ferrierite zeolites is presented in detail.
(Paper I)

Propene desorption over the zeolite catalysts studied has been observed to decrease in the
following order: ZSM-5 > Pt/ZSM-5 > Pt/Beta > Beta >> Pt/Y zeolite > Y zeolite >
Ferrierite ≈ Pt/Ferrierite. In the case of propene and oxygen, the order of the propene
desorption is different from that of the pure propene adsorption. The order was the
following: Pt/ZSM-5 > Pt/Beta >> Beta > ZSM-5 > Ferrierite ≈ Pt/Ferrierite > Pt/Y
zeolite. The parent Y zeolite did not show any adsorption capacity of propene with excess
oxygen (Figure 21).
 53

ZSM-5 4e-6 Y

Desorption rate [a.u]

Beta Fer
1,6e-3 3e-6
Y Pt-Y
Fer Pt-Fer
Pt-ZSM-5 2e-6
Desorption rate [a.u.]

Pt-Beta
1,2e-3 Pt-Y
1e-6
Pt-Fer

0
8,0e-4 0 100 200 300 400 500 600

4,0e-4

0,0
0 100 200 300 400 500 600
Temperature [°C]

Fig. 21. Propene desorption bands over the parent and 1 wt-% Pt-loaded zeolites. A
C3H6+O2-TPD study. In the interior graph desorption over the parent and Pt-loaded Y and
Ferrierite zeolites is presented in detail. (Paper I)

0,20
NO
C3H6 [pro]
0,15
C3H6 [pro+O2]
Integrated areas [a.u.]

0,10

0,01

0,00
-5 B et
a Y FER -ZSM-5 Pt-Beta Pt-Y Pt-FER
ZSM Pt

Fig. 22. Comparison of the calculated desorption amounts of NO and C3H6 during the NO-,
C3H6-, and C3H6 + O2 -TPD experiments (Paper I).

In Figure 22 the comparison of calculated desorption amounts of NO and propene during

the NO-, C3H6-, and C3H6 + O2 -TPD experiments is presented. The areas are calculated
 54
by the SigmaPlot software using trapezoidal approximation (SigmaPlot Tutorial). It can
be observed that the ZSM-5- and Beta-based zeolite catalysts adsorbed significantly
higher amounts of propene than Y and Ferrierite zeolites. The 1 wt-% Pt/ZSM-5 is
observed to adsorb NO most efficiently. The Y zeolite and Ferrierite showed rather small
adsorption capacity of propene. All the platinum-loaded zeolite catalysts are found to
adsorb more NO than the parent zeolites.

5.5 Acidity measurements

The acidic properties of zeolite catalysts have a significant role in the reduction of NOX
by propene as suggested by Gerlach et al. (1999a and 1999b). In Figure 23 the pyridine
adsorption over the parent and 1 wt-% Pt loaded ZSM-5, Beta and Y zeolite catalysts is
presented. The first spectra of each figure (a-f) show the adsorption bands after 4 minutes
of pyridine adsorption. The other spectra are taken after evacuation at 150°C for 30
minutes, 250°C for 60 minutes, and 350°C for 60 minutes. In the case of the 1 wt-%
Pt/Beta and Pt/Y the spectra after the last evacuation were not recorded because pyridine
was detected being desorbed after 60 minutes of evacuation at 250°C. The acidic
properties of Ferrierite and 0.8 wt-% Pt/Ferrierite have not been measured.
The analyses of the spectra have been based on the comparison of the experimental
bands with the observations of other research groups reported in the literature.
A negative band at around 3605 cm-1 can be assigned as acidic hydroxyls on the
Brønsted acid site (Al-(OH)-Si). The band can be observed over ZSM-5-based zeolite
catalysts. However, over the other samples the band was almost insignificant. The band
caused by silanol groups at around 3740 cm-1 was detected over all the catalysts studied.
(Maache et al. 1991) In the case of Y and Pt/Y zeolite catalysts the hydroxyl group was
detected to be the weakest. The intensity changes of the bands at the OH-region were not
significant during the evacuation period over ZSM-5-based catalysts, while over the
Beta-based catalysts the negative band disappeared.
The adsorption of pyridine is detected at the wavenumbers of 1545, 1490, and
1450 cm-1. The band at around 1450 cm-1 can be assigned as pyridine adsorbed on Lewis
sites. The band at 1545 cm-1 is assigned to pyridine on the Brønsted acid sites, and
1490 cm-1 is due to the adsorption of pyridine on both Brønsted and Lewis sites. The
Lewis sites represent the framework Al in the zeolites. (Bortnovsky et al. 2001)
The adsorption of pyridine on the Pt-loaded Y zeolite causes bands only at 1596 and
1445 cm-1. The band at 1445 cm-1 indicates pyridine adsorbed on weak Lewis acid sites.
The very weak band at 1541 cm-1 (Brønsted acid site) disappeared after evacuation at
150°C for 30 minutes. Janin et al. (1991) have obtained the same type of results in their
study over the dealuminated HY zeolite.
The strongest adsorption bands are detected over the parent and 1 wt-% Pt/ZSM-5.
The Beta and 1 wt-% Pt/Beta showed pyridine adsorption bands at Lewis and Brønsted
acid sites at 150°C. Above 150°C the adsorption bands were insignificant. The same
phenomenon can be measured over the 1 wt-% Pt/Y zeolite, however, the parent Y zeolite
does not indicate any pyridine adsorption.
 55

(a)

1490
0.25 a.u.

1637
1623
1546
IV

3104
3073
3140

2979

1453
3176
3264
Adsorbance [a.u.]

III

II

I
3746

3611

3800 3600 3400 3200 3000 2800 1800 1600 1400

W avenumber [cm-1]

(b)
0.25 a.u.

IV
3092
3136
Adsorbance [a.u.]

III
1596

1444
1536

II

I
3722

3800 3600 3400 3200 3000 2800 1800 1600 1400

W avenumber [cm-1]

(c)

IV
Adsorbance [a.u.]

III

II
1540
1444
1596

I
3748

3800 3600 3400 3200 3000 2800 1800 1600 1400

W avenumber [cm-1]
 56

d)

1490
0.25 a.u.

1640

1545
1628
3073
3104
IV

3140

2977
3176
3264
Adsorbance [a.u.]

III

II

I
3607

3800 3 600 34 00 3200 3000 280 0 1800 16 00 1400

W a ven um be r [cm -1 ]

(e)
0.25 a.u.
3078
3142

2977
3176

IV (not m easured)
3264

1491
Adsorbance [a.u.]

III 1596

1444

II

I
3734

3800 3600 3400 3200 3000 2800 1800 1600 1400

W avenum ber [cm -1 ]

(f)
0.2 5 a .u.

IV (no t m easu re d)
III
Adsorbance [a.u.]

1596

1445

II
3739

1541

38 00 36 00 3 40 0 32 00 30 00 2 800 18 00 1 600 14 00

W avenumber [cm -1 ]

Fig. 23. DRIFT spectra of pyridine adsorption over the parent ZSM-5 (a), Beta (b), Y (c) and
the 1 wt-% Pt-loaded ZSM-5 (d), Beta (e) and Y (f) zeolites. Spectra have been taken after (I)
pyridine adsorption at 150°C for 4 minutes, (II) evacuation at 150°C for 30 minutes, (III)
evacuation at 250°C for 60 minutes, and (IV) evacuation at 350°C for 60 minutes.
 57
The adsorption of pyridine on the strong Brønsted acid sites on ZSM-5 and 1 wt-%
Pt/ZSM-5 was observed to remain irreversible during heating and evacuation. It can be
concluded that the interaction of pyridine with the acidic sites of the ZSM-5 is strong
enough to prevent the high mobility of the adsorbed pyridine. Bludau et al. (1998) have
reported similar results.
Based on the observations of the IR spectra the total amount of Brønsted acid sites was
found to be equivalent between the parent and corresponding Pt-loaded ZSM-5 and Beta
zeolite catalysts as reported recently also e.g. by Villegas et al. (2005) and Halász et al.
(2004). In the case of Y zeolite the pyridine adsorption was observed to be very low. The
acidity of the zeolite catalysts studied can be detected to decrease in the following order:
Pt/ZSM-5 ≈ ZSM-5 > Pt/Beta ≈ Beta > Pt/Y > Y zeolite.
 6 Reaction mechanisms and kinetics

6.1 Proposed reaction mechanisms from literature

Several proposals have been presented in the literature for the mechanism of the SCR
reaction over zeolite- and Al2O3-based catalysts. Cu-MFI was one of the first catalysts
studied for the HC-SCR of NOX. After that different mechanisms have been proposed for
the SCR reaction. Reaction intermediates such as isocyanates (-N=C=O), cyanides
(-CN-), nitriles, organic nitro (-ONO) and nitrite (-NO2) as well as dinitrogen (-NN-)
species have been introduced and studied by the IR technique. The proposed steps are 1)
NO dissociation, 2) partial oxidation of hydrocarbon to CXHYOZ species, 3) formation of
organonitrogen compounds, and 4) NO oxidation to NO2. (Hoost et al. 1995a, Hamada
1997, Cant & Liu 2000)

6.1.1 PGM/Al2O3-based catalysts

Several research groups have studied the Al2O3-based catalysts for the HC-SCR of NOX.
Numerous reaction mechanisms and kinetic models have been proposed for NOX
reduction by propene/propane over PGM-loaded catalysts. According to Burch the NO
reduction by propane over Pt/Al2O3 goes via the dissociation of adsorbed NO. The
species formed can further react to molecular nitrogen or nitrous oxide. Propane
undergoes a dissociative oxidation with oxygen from NO or O2 eventually producing CO2
and H2O. (e.g. Burch & Watling 1997, Bamwenda et al. 1995)
The reaction mechanisms over Pd/Al2O3 have been proposed to go via isocyanate
formation, which can further react with NO, NO2 or atomic oxygen. Shimizu et al. (1998)
reported acetate formation over alumina catalysts. Acetate and nitrate species on the
catalyst support can react and form N2, CO2, CO, and H2O. (Shimizu et al. 1998)
The mechanistic approach by Praserthdam et al. (2002) over the Pt-loaded Al2O3
catalysts proposed the NO dissociation and reaction with NO to N2 and N2O.
Organonitrogen species have also been proposed to be as intermediates in the reduction
of NO. (Praserthdam et al. 2002)
 59

6.1.2 Pt-loaded zeolite catalysts

The reaction mechanisms for NOx reduction over zeolite-based catalysts have been
proposed to go via -NCO, -CN, -ONO- or -NHx intermediates formation (Hoost et al.
1995a, Amiridis et al. 2004). In the case of high-silica zeolite materials the reaction
routes via the -NCO intermediate formation are not introduced so often. One reason for
this can be that silica does not adsorb -NCO but alumina does, so there is a lack of
evidence for -NCO species on the zeolite surfaces. (Burch et al. 2002)
Deeba et al. (1999) have proposed the platinum sites as being responsible for the NO
reduction at temperatures above 250°C. The hydrocarbon mitigation at lower
temperatures might be due to the storing capacity of the acidic sites of the zeolite support
forming hydrocarbon species. These species are independently active for the NO
reduction. (Deeba et al. 1999)
According to the study of Xin et al. (1997b), the reaction mechanism of NO reduction
over Pt/ZSM-5 in the case of NO+C3H6+O2 is suggested to have three major steps: the
adsorption and/or decomposition of reactants, the oxidation of surface organic
compounds, and the formation of reduced products. NO and O2 are assumed to dissociate
to N and O species on Pt. Pt-O can react with adsorbed propene (π-allyl) surface species
forming partially oxidised hydrocarbon compounds. (Xin et al. 1997b)
Rottländer et al. (1996) have presented a similar proposition for NOX reduction by
propane and propene over Pt/ZSM-5. They suggest that the reaction between propene and
surface oxygen species form CXHY(OZ) compounds. At the same time NO was proposed
to react on oxidised Pt to NO2. The hydrocarbon intermediates formed react either non-
selectively with O2 to CO2 or selectively with NO to the desired products (CO2, H2O, N2).
(Rottländer et al. 1996)
In lean conditions NO and O2 compete for the sites of dissociative adsorption on the
Pt surface. The role of hydrocarbon is proposed to be a clean-off agent by removing the
atomic oxygen adsorbed on the Pt surface sites. The dissociation of NO is also reported to
be slower than the dissociation of oxygen. (García-Cortéz et al. 2003a & 2003b, Burch &
Scire 1994) At high temperatures the dissociation of NO on Pt is more effective, while at
low temperatures only a part of NO is dissociated. The formation of N2O on the Pt-loaded
catalysts can thus be explained with the reaction between adsorbed NO and formed N
species. (Pérez-Ramírez et al. 2001)
Platinum-loaded Beta zeolite has been studied in the SCR of NOx in lean conditions
quite recently. Pt-loaded Beta has been found to be a very effective catalyst for the SCR
of NO by propene in the presence of excess oxygen. (Bueno-López et al. 2004)
The formation of NH4+ species over the Pt-loaded ZSM-5 in the excess oxygen has
been introduced by Satsuma et al. (2003). They proposed that the formed NH4+ reacts
with NO over acid sites. The proposition also pointed out that the formation of the
undesired by-product (N2O) could be avoided.
NaY zeolites have been studied in the reduction of NO2 by propylene. Li et al. (2005)
proposed that NO is oxidised to NO2 and it further reacts with hydrocarbon species. The
reaction mechanism introduced suggests that the reactions between NO2 and propylene
produce oxygenated hydrocarbons (e.g. C3H6O) and NO. (Li et al. 2005)
 60
Gerlach et al. (1999a) have studied the reaction between propene and NO over H-
Mordenite. They have suggested that NO reacts with zeolites’ Brønsted acid sites,
producing NO+ ions. The reaction of NO+ with propene can furthermore produce organic
nitro compounds, which can be transformed to propenal oxime and, finally, acrylonitrile.
NO reduction by hydrogen over Pt-Na/ZSM-5 has been studied by Machida et al.
(2004). They reported that the Brønsted acid sites in the zeolite activate hydrogen
molecules. Thus, in the reduction of NO in a NO-H2-O2 gas mixture the reaction between
activated hydrogen and NO2- produces molecular nitrogen more selectively. (Machida et
al. 2004)
The coupling of nitrogen atoms is presented as a prerequisite for the molecular
nitrogen N2 and nitrous oxide (N2O) formation. The coupling effect has been reported by
isotope labelling experiments carried out by e.g. Acke & Skoglundh (1999).
DRIFT studies of adsorption of hydrocarbons on the zeolite surface have been carried
out and the adsorption bands of hydrocarbon groups have been reported by e.g. Bolis et
al. (1980).

6.2 Reaction mechanisms

In our study, the experimental adsorption bands (e.g. wavenumbers) were analysed and
compared with similar spectra and the adsorption bands presented in the literature. The
possible adsorbed surface species as well as intermediates could thus be identified. The
reaction mechanistic steps were then formed based on the experimental observations and
recent literature.

6.2.1 Pd/Al2O3-based catalyst

The data obtained over the Pd/Al2O3-based catalysts from DRIFT and activity
experiments was used to build reaction mechanisms for the reduction of NO and for the
oxidation of propene in lean to rich conditions. The possible reaction mechanism of NO
reduction by propene over the pre-oxidised Pd/alumina-based catalysts is presented in
Table 6 (Paper V).
The acetates and formates detected on the catalyst surface provide evidence of the
reaction mechanism that goes via the reaction between partially oxidised hydrocarbons
and NO (Fritz & Pitchon 1997, Tanaka et al. 1994). The formation of isocyanate as a
surface intermediate is also observed in our study. The other possible reaction route goes
via the formation of isocyanate and cyanide species by the reaction with NO to N2. (Fritz
& Pitchon 1997, Paper V)
The most probable reaction route is initiated by the adsorption of NO and propene, and
then adsorbed propene reacts with the surface oxygen to partially oxidised hydrocarbons
(CxHyOz). These compounds can then react with NO or oxygen and form organic nitro
compounds, acetates, formates, and isocyanates, which were detected as surface
intermediates in the DRIFT measurements. The reaction between nitrates and isocyanates
or cyanides produces nitrous oxide and the desired final products (N2 and CO2).
 61
Table 6. The observed reaction intermediates and products for NO, C3H6, and/or O2
reactions (1 and 3% Pd-catalysts); reaction mechanism approach (Paper V).
Reaction Observed at/by Refs in Paper V
NO adsorption and reactions
NO + * ↔ NO* 1630 cm-1 12, 19, 20
NO* + * → N* + O* n.d. 12, 19, 20
NO* + N* → N2O Gas analysis 11, 12, 18
NO* + O* ↔ NO2* 1320-1250 cm-1 20
NO* + O2 → NO3* 1300-1250 cm-1 4
Propene adsorption and reactions
C3H6 + * → CxHy* 3200-2900 cm-1 3, 21
CxHy* + O2 / O* → CxHyOz* 1565, 1395 cm-1 21
CxHy* + NO → -CH2-NO* 1658 cm-1
-CH2-NO* → -C≡N* + H2O 2160 cm-1 5
CxHy* + NO2* → -CH2-NO2* 1658 cm-1 5, 17
CxHyOz + NO* → -CH2-NO2* 1658 cm-1 5
-CH2-NO2* → -CH2-C=N=O* 2252-2230 cm-1 5
-CH2-C=N=O* → -CH2-N=C=O* 2252-2230 cm-1 5
Cyanide/isocyanate reactions
-NCO* + NOx* → N2 + CO2 + N2O Gas analysis 2, 17, 20
-C≡N* + NOx* → N2O + N2 + CO2 Gas analysis 21
N2O* + CO* → N2 + CO2 Gas analysis 12
-NCO* + H2O → NH3 + CO2 Gas analysis 17
-C≡N* + H2O → NH3 + CO Gas analysis 22
n.d. = can not be detected by the FTIR method
X* = adsorbed species, * = vacant site

The reaction mechanistic hypothesis for NO reduction by CO has been introduced in

Table 7 (Paper IV). The formation of isocyanate species was observed experimentally to
be very strong. The interaction between CO and formed nitrates as well as nitrites
produced isocyanate. The reaction mechanistic model was derived and the results give
evidence of the role of isocyanates in the reduction of NO.
 62
Table 7. The reaction mechanistic approach for NO reduction by CO (Paper IV).
Reaction Mechanism
A B C
NO + * ⇄ NO* + + +
CO + * ⇄ CO* + + +
O2 + 2 * ⇄ 2 O* + + +
CO* + O* → CO2 + 2* + + +
NO* + * → N* + O*
NO*+ CO* → CO2 + N* + * +
NO* + N* → N2O + 2 * +
2 N* → N2 + 2* +
NO* + CO* → NCO*+ O* +
NCO* + NO* → N2 + CO2 + 2*
NCO* + NO* → N2O +CO* + * +
2 NO* → N2O* + *O
N2O* ⇄ N2O + *
N2O* → N2 + O*
2 NO* → (NO*)2
(NO*)2 → N2O + O* + *
(NO*)2 → N2 + 2 O*
2 NO* → N2O + O* + * +
2 NO* → N2 + 2 O* + +
X* = adsorbed species, * = vacant site

It can be concluded that palladium on Al2O3-based support is a good catalyst for the
reduction of NOx and at the same time for the oxidation reactions of propene and CO in
the conditions studied.

6.2.2 Pt-loaded zeolites

In Table 8 the surface and free intermediates as well the observed products over 1 wt-%
Pt/ZSM-5 are presented (Paper III). The reaction mechanistic steps are formed by the
observed surface intermediates and compared with information from recent literature
(e.g. Gerlach et al. 1999, Poignant et al. 2001, Burch et al. 2002, Xin et al. 1997a &
1997b).
 63
Table 8. Identified surface and free intermediate species over 1 wt-% Pt/ZSM-5 under
reaction conditions (1000 ppm NO, 1000 ppm C3H6, and 5% O2); comparison with the
literature data (Paper III).
Reaction Observed at / by Refs in Paper III
NO + * → NO* 1820, 1935 cm-1 1, 6
NO* + * → N* + O* n.d. 7
O2 + * → O2* n.d. 7
O2* → 2 O* n.d. 7
NO* + O2* → NO3* 1310-1290 cm-1 2, 6
NO* + O* → NO2* 1658, 1310-1290 cm-1 2, 6
NO* + N* → N2O* 2234 cm-1 7
NO* + NO* → N2O* + O* 2234 cm-1 7
C3H6 + * → C3H6* 1642, 1507 cm-1 1, 9
C3H6* + n* → n CxHy* 3200-2800 cm-1 2
CxHy* + NO* → C3H7 -ONO* 1662 cm-1 9
C3H6* + NO* → C3H4NOH* 1414, 1460 cm-1 1
C3H4NOH* → C2H3CN* + H2O* 2280 cm-1 1
CxHy* + Oz* → CxHyOz* 1595 cm-1 2
CxHyOz* + Oz* → CO* + H2O 2070-2050, 1190 cm-1 8, 13
C2H3CN* + 2 H2O* → NH3* + C2H3COOH* 3265 cm-1 1, 14
NH3* + NO* → N2 + H2O gaseous
CxHy* → C3H8 gaseous
NO2* → NO2 + * gaseous
N2O* → N2O + * gaseous
CO* → CO + * gaseous
CO* + O* → CO2 + 2* gaseous
n.d. = can not be detected by the FTIR method
X* = adsorbed species, * = vacant site

The adsorbed reactants and the surface intermediates formed can provide information on
possible reaction routes in selective catalytic reduction of NO by propene in the presence
of excess oxygen at low temperatures.
Adsorbed nitrite and nitrate species, hydrocarbon species and partially oxidised
hydrocarbons (CxHyOz) can be detected over the platinum-loaded zeolite catalysts. The
reactions between adsorbed species produce desired products (CO2, H2O, and N2). In
addition, at around the light-off temperature the undesired by-products such as nitrogen
dioxide, nitrous oxide, and carbon monoxide can be detected in the gas phase.
In the proposed reaction mechanism, it is assumed that NO is adsorbed on Pt sites, and
acidic sites of ZSM-5 are active for both NO and hydrocarbons adsorption. NO and
hydrocarbons are oxidised to nitrates, nitrites and partially oxidised hydrocarbons,
respectively. The reaction between adsorbed NOX and cracked or partially oxidised
hydrocarbon species occurs on the Pt-sites producing organic nitro- or nitroso-
compounds. The reduction of NO is proposed to happen both on the acidic sites of ZSM-
5 at low temperatures as well as on the Pt-sites at higher temperatures. The Pt-sites are
 64
active in promoting NO2 formation, which can have an effect on the adsorption of
hydrocarbons.
The study of NOX abatement by hydrocarbon-assisted selective catalytic reduction
over the Pt-loaded ZSM-5 zeolite catalyst gives guidelines for the development of more
effective catalytic materials for exhaust gas purification. Furthermore, the proposed
reaction mechanism gives the possibility to derive the mechanistic kinetic model for the
C3H6-SCR of NO over the zeolite catalysts.
In Table 9 the reactions that are probably present in the reaction mechanism of C3H6-
SCR of NO over Pt-loaded zeolite catalyst have been introduced. Three different
hypotheses for the possible reaction mechanism have been derived. Hypothesis A
contains only the reactions between NO or propene with O2. In hypothesis B the reactions
between NO and C3H6 have been included and in hypothesis C the NO2 as an oxidant has
also been considered. In the table the CxHy-species are marked as C3H6, C2H4, and CH2 to
make the reaction mechanism atom balance equal. Thus, CH2 can be assigned as CH3
species as well. The reactions (e.g. H+ addition) which can be due to the acidic properties
of the zeolitic support are also neglected. To keep the mechanism as simple as possible,
the formation of carbocations is not included in the reaction. The author is, however,
aware that e.g. C3H7-ONO surface intermediates are reported to be formed over e.g.
ZSM-5 zeolite catalysts.
 65
Table 9. The possible mechanistic steps for the C3H6-SCR of NO over Pt-zeolite catalysts.
Reaction Mechanism
Hyp. A Hyp. B Hyp. C
NO + * ⇄ NO* + + +
C3H6 + * ⇄ C3H6* + + +
O2 + 2* ⇄ 2O* + + +
NO2* ⇄ NO2 + * + + +
CO* ⇄ CO + * + + +
NO* + * ˆ N* + O* + + +
NO* + O* ˆ NO2* + * + + +
NO* + N* ˆ N2O + 2* + + +
N* + N* ˆ N2 + 2* + + +
C3H6* + O* ˆ C3H6O* + * + + +
C3H6O* + O* ˆ C2H4O* + CH2O* + + +
C2H4O* + O* ˆ 2 CH2O* + + +
CH2O* + O* ˆ CO* + H2O + * + + +
CO* + O* ˆ CO2 + 2* + + +
C3H6* + NO* ˆ C3H6NO* + * + + +
C3H6NO* + NO* ˆ N2 + C2H4O* + CH2O* + +
C3H6O* + NO* ˆ C3H6NO2* + * + +
C3H6NO2* + NO* ˆ ONC3H6NO2* + * + +
ONC3H6NO2* + * ˆ N2 + C2H4O* + CH2O2* + +
C2H4O* + NO* ˆ C2H4NO2* + * + +
CH2O* + NO* ˆ CH2NO* + O* + +
C2H4NO2* + NO* ˆ N2O + 2 CH2O* + * + +
CH2NO* + NO* ˆ N2O + CH2O* + * + +
CH2NO* + NO* ˆ N2 + CH2O2* + * + +
CO* + NO* ˆ CO2 + N* + * + +
CH2O2* + O* ˆ CO2 + H2O + 2* + +
CO* + NO2* ˆ CO2 + NO* + * +
C3H6* + NO2* ˆ C3H6NO2* + * +
C3H6NO2* + NO2* ˆ C2H4NO2* + CH2NO2* +
C3H6NO* + NO2 * ˆ ONC3H6NO2* + * +
C3H6O* + NO2* ˆ C3H6NO2* + O* +
C3H6O* + NO2* ˆ C3H6O2* + NO* +
C3H6O2* + * ˆ C2H4O* + CH2O* (fast) +
C2H4O* + NO2* ˆ C2H4NO2* + O* +
C2H4O* + NO2* ˆ C2H4O2* + NO* +
C2H4O2* + * ˆ 2 CH2O* (fast) +
CH2O* + NO2* ˆ CO2 + H2O + N* + * +
CH2O* + NO2* ˆ CO* + NO* + H2O +
C2H4NO2* + NO2* ˆ 2 CH2NO2* +
CH2NO2* + NO2* ˆ CO2 + H2O + N2O + 2* +
CH2NO* + NO2* ˆ N2O + CH2O2* + * +
CH2NO2* + NO* ˆ N2 + CO2 + H2O + 2* +
X* = adsorbed species, * = vacant site
 66
The reactants adsorbed on the catalyst surface and these adsorbed species were detected
by Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS). The desired
gaseous (e.g. CO2, H2O) and other reaction by-products and/or intermediates (e.g. CO,
NO2, and N2O) were detected by the gas FTIR technique. Homonuclear diatomic
molecules like molecular nitrogen (N2) cannot, however, be detected by the IR technique.
The experimental observations used to build a plausible reaction mechanism for the
C3H6-assisted selective catalytic reduction (SCR) of NOX over platinum-based zeolite
catalysts can be presented as shown in Figure 24 (Paper III).

oxid.
O2 Oz* CO* CO2
oxid.
des. CO
CxHyOz*
C3H6 H2O,
+NOX CO2
CxHy*
R-ONO*
R-NOH* via NH3+
NO formation
NO2*
oxid.
NO3* +NOX N2,
NO* CO2
N* NO2 H2O
des.
180-320 °C
N2O

Fig. 24. A plausible reaction mechanism for the C3H6-SCR of NOX over Pt-loaded zeolite
catalysts (Paper III).

The results reported in the literature were used as reference data in the analysis of the
observed adsorption bands. The inlet gas components (NO, C3H6, and O2) were first
adsorbed on the catalytic active sites. The adsorbed species were then reacting with each
other, forming partially oxidised hydrocarbons, nitrate, and nitrite species. Furthermore,
partially oxidised hydrocarbons and nitrogen species can form organic nitro compounds
(R-ONO and R-NOH). These organic nitro species in turn can produce e.g. ammonium
ions, which can react with NOX to form N2 and H2O. Nitrogen oxides were assumed to
desorb or react with N* atoms or organic nitro species, forming N2, N2O, CO2, and H2O.
All of the mechanistic steps are not presented in Figure 24 because of the multiple
reaction pathways and complexity of the reactions between various adsorbed surface
species as well as the reactions between gaseous and adsorbed molecules.

6.3 Kinetic studies

The reaction kinetic model based on the activity and DRIFT studies has been derived for
NO reduction by CO over Pd/Al2O3-based (Paper IV) and by propene over Pt/zeolite
catalysts. A pseudo steady-state one-dimensional plug-flow (fixed bed) reactor model was
 67
used (Monnerat et al. 2003, Maunula et al. 2000). A steady-state operation was assumed.
A non-linear regression analysis was used for the parameter estimation. The Nelder-Mead
simplex and the Levenberg-Marquardt algorithms were used in the parameter estimation
(Nelder & Mead 1965, Marquardt 1963). The system of ordinary differential equations
was solved by a stiff ODE solver (LSODE) using the backward difference method
(Hindmarsh 1980). The axial dispersion was neglected and the reactor was assumed to
operate in isothermal steady-state conditions. External and internal heat transfer was also
neglected.

6.3.1 NO reduction by CO over Pd/Al2O3-based catalysts

Three different mechanisms were compared: direct decomposition (A), bimolecular

reaction (B) and N2O formation via isocyanate complex formation (C). The mechanisms
are presented in Table 7, Chapter 6.2.1 (Paper IV). The first mechanism, A, presents the
regenerative mechanism in which CO reacts with adsorbed oxygen on the surface formed
in NO decomposition (steps marked in Table 7). Mechanism B is an example of a
coupled mechanism, in which NO decomposition is assisted with CO. Mechanism C is a
combination of the two previous mechanisms.
The frequently used presumption of dissociative adsorption of O2 was used based on
the low desorption rate of oxygen at temperatures below 400°C on the catalyst (Harmsen
et al. 2001, Mukadi & Hayes 2002, Oh et al. 1986). The steady-state kinetic model is
derived and reported in detail in Paper IV.
In principal, reaction rate parameters are temperature dependent by the Arrhenius law
and the temperature dependence of the equilibrium constants follows the Gibbs-Hemholtz
equation. The assumption that the reaction enthalpies are temperature independent results
in the fact that the same functional form (exponential function) for temperature
dependence of all the parameters can be used. In addition, the mean temperature reaction
rate constants and equilibrium constants were used instead of pre-exponential
coefficients, and the standard re-parameterisation was applied.
The calculated parameter values are presented in Table 10 (Paper IV). The maximum
number of adjustable parameters was 16, but several of the parameters could be ignored.
The neglected parameters are expectedly the ones that describe the temperature
dependence or the adsorption limitations. The estimated parameters are in the physically
meaningful domain and the magnitude of the parameters is typical for the type of
catalyst, e.g., adsorption enthalpies are non-positive and the activation energies of the
catalytic reactions are tens of kJ. However, the activation energy of oxygen adsorption
was relatively high (approx. 20 kJ/mol). The mass transfer limitations were not taken into
account in the reactor model.
 68
Table 10. The calculated parameters for the kinetic models of NO reduction by CO in the
three mechanisms studied (see Table 7).
Direct decomposition, A Bimolecular, B Isocyanate formation, C
Param. Value Std. Param. Value Std. Param. Value Std.
error error error
k6 2.30 m3/kgs 12.6 kb9 380 m3/kgs 10.3 k6 0.79 m3/kgs 0.3
Ea, 6 22.7 kJ/mol 16.3 Ea, b9 46.2 kJ/mol 2.8 Ea, 6 21.0 kJ/mol <0.1
k21 14.1 m6/molkgs 13.3 kb10 0.260 mol/kgs 18.4 kc12 3.15 m6/molkgs <0.1
6
k22 13.0 m /molkgs 13.6 Ea, b10 20.8kJ/mol 10.0 Ea, c12 1.75 kJ/mol 73.8
Ea, 22 46.9 kJ/mol 4.4 kb7 254 m4½/mol½kgs 10.4 kc22 4.69 m6/molkgs 0.1
Ka2 5.98 m3/mol 50.0 Ea, b7 31.2 kJ/mol 5.5 Ea, c22 49.7 kJ/mol <0.1
Ha2 -37.5 kJ/mol 15.7 KNO 0.24 m3/mol 19.7 Kc1 1.5 m3/mol 15.8
3 3
KNO 45.0 m /mol 15.8 KCO 205 m /mol 5.6 Hc1 -17.9 kJ/mol 39.0
HNO -9.31 kJ/mol 12.8 Kb1 115 m3/mol 22.8 Kc2 1.0 · 10-4 0.4
KCO 7.0 m3/mol 30.2 Kb2 0.043 32.0 Kc3 22.0 m3/mol 0.1
Hb2 11.7 kJ/mol 17.5 Hc3 -16.6 kJ/mol 0.1
Std. error = standard error (%)

Pore diffusion has slight, if any, effect within the temperature range used because of the
thin (20 μm) washcoat layer of the monolith catalyst. However, as the temperature, and
reaction rate, increase, the influence of mass transfer increases rapidly (Massing et al.
2000, Duprat 2002). Only minor differences exist between the model and the gas phase
concentrations measured between the three models. The evaluation is made by comparing
the simulated concentration curves with the experimental values and deriving the R2
values of the estimations. An example of the calculated (direct decomposition model) vs.
experimental gas-phase concentrations is shown in Figure 25. The data was taken from
the experiments performed in lean conditions. Model A predicts the observed
experimental data quite well.
 69

Concentration [ppm]

Temperature [°C]
Concentration [ppm]

Temperature [°C]

Fig. 25. Example of the experimental CO (∗), NO (×) and N2O (V) concentrations and the
calculated values (solid line) of the direct decomposition model (A) in lean a) NO-CO and b)
NO+CO+O2 conditions.

By comparing the simulated surface coverages to the semi-quantitative adsorption

amounts (Paper IV), it can be postulated that the bimolecular reaction mechanism is not
the main reaction pathway. The coverage predicted by the direct decomposition reaction
(A) and reaction via isocyanate (C) includes the same kind of features as the measured
adsorption values. Neither mechanism can predict the increase in NO coverage in the
absence of CO, because NO decomposition is proposed to be irreversible. The other parts
of the NO coverage are predicted correctly by the direct decomposition model. The
isocyanate measured by DRIFT is adsorbed on the support rather than on platinum group
metal clusters. Thus, it is postulated that it is advantageous to construct models on NO
reduction over the Pd-containing catalysts based on direct decomposition mechanisms
(A). The kinetic model can be modified by considering the equilibrium limitation of NO
decomposition, which takes into account the increase in the NO coverage in addition to
the increase in the oxygen coverage, when the amount of CO is insufficient. However, it
 70
should be considered in each application if the benefits of the equilibrium limited NO
decomposition step is greater than the drawbacks of the increasing model complexity.
The results of the modelling give evidence that the most probable NO reduction route
over the Pd-containing catalysts goes via the direct decomposition mechanism
(mechanism A, Table 7). The main role of the reductant was to regenerate the oxygen-
covered surface. The evidence of isocyanate as an intermediate to nitrous oxide was not
found based on the modelling done. However, strong isocyanate formation on the surface
of the support material was detected. The formation causes slow transient effects above
the light-off temperature, which might reduce emissions during the catalyst warm-up.
DRIFT measurements did not give a complete structural guidance for the reaction steps,
but knowledge of surface intermediates facilitates the model construction and
discrimination. However, more activity data (e.g. isotopic labelling and transient
experiments) is still needed to support the plausible kinetic model.

6.3.2 Hydrocarbon-assisted NO reduction

The activation energies, Ea, for the NO reduction and propene oxidation in the lean
conditions over the 1 wt-% Pt-loaded ZSM-5, Beta, Y, and 0.8 wt-% Pt-Ferrierite were
calculated by the Arrhenius equation. The light-off curves i.e. conversion versus
temperature plots of the NO and propene were used as the data source for the
calculations. The NO reduction rates were calculated from measurements of differential
NO conversions by the equation (1) (Duprat 2002, Massing et al. 2000, Captain et al.
1998, Roberts and Amiridis 1997)

rNO=FNOxNO/mcat, (1)

where the NO reduction rate is rNO (mol/g s), FNO is the molar inlet rate of NO (mol/s),
xNO is the fractional conversion of NO and the mass of the catalyst in the reactor is
denoted as mcat (g). The logarithmic reduction and oxidation rates versus temperature
were drawn. The regression lines were fitted in the range below the maxima of the NO
reduction. The determination coefficient (R2) of the regressions was good in all cases but
two. For the propene oxidation the average activation energies (Ea, C3H6) were 165±7,
115±3, 114±9, 134±20 kJ/mol over the 1 wt-% Pt-loaded ZSM-5, Beta, Y, and Ferrierite
zeolite catalysts, respectively. The average activation energies for the NO reduction
(Ea, NO) were 104±8, 105±9, 136±1 and 154±15 kJ/mol, respectively. The calculated
values are in line with the activation energies reported in the recent literature over several
catalysts i.e. for propene oxidation 107-151 kJ/mol and for NO conversion in the range of
72-182 kJ/mol (e.g. Bueno-Lopez et al. 2006 Botas et al. 2001, Ioan et al. 2005).
The reaction mechanism of the NO reduction by propene in excess oxygen over
zeolite-based catalysts has been derived (see Table 9 proposed reaction mechanisms from
A to C) and the kinetic modelling will be done in the next research step. The mechanistic
models still need assumptions to be done to facilitate the kinetic modelling.
Discrimination between the importance of each mechanistic step can further be supported
by data from transient and isotopic labelled experiments.
 7 Discussion
The reduction of NO by propene over the parent and 1 wt-% Pt-loaded zeolite and the 1
and 3 wt-% Pd/Al2O3-based catalysts have been studied and compared. For the reaction
mechanisms the DRIFT technique was used to detect the surface species that were
adsorbed and formed. The gaseous products were analysed in the activity experiments by
gas FTIR.
The EFTEM experiments of the Pt-loaded zeolite catalysts give evidence of the large
(5-10 nm) extraframework platinum particles. These Pt clusters can be assumed to act as
one type of the active sites of the catalysts. The Pt dispersions of the catalysts were
detected to be around 12%, except for 0.8 w-% Pt/Ferrierite around 33% (see Table
4).The small platinum particles inside the pores were not detected, but they have an effect
on catalytic activity because the pores of the zeolite materials used are large enough for
the inlet gas molecules to enter into the pores and for the product molecules to exit. This
was testified by the N2 adsorption experiments and the mean pore sizes of the zeolite
materials.
In the activity tests propene reached a conversion of >99% over all the Pt-loaded
zeolite catalysts with the inlet gas mixture containing excess oxygen. The light-off
temperatures of propene over the 1 wt-% Pt-loaded ZSM-5, Beta, Y, and Ferrierite were
253, 208, 198, 227ºC, respectively. When comparing the T50 values of propene
conversions over the parent zeolites and the 1 wt-% Pt-loaded zeolites, the reverse order
of the materials can be observed. Platinum can be detected to have a minor effect on
propene oxidation in the case of ZSM-5 and Ferrierite-based zeolites, but the most
significant effect on the light-off temperature of Y- and Beta-based zeolite catalysts. This
phenomenon can possibly be due to the smaller average pore size of Ferrierite and ZSM-
5 zeolites resulting in a smaller decrease in the light-off temperature of propene over the
Pt-loaded Ferrierite and ZSM-5.
Nitric oxide did not exceed 50% conversion over the 1 wt-% Pt/ZSM-5 and
Pt/Ferrierite catalysts, while the best conversions were observed over the 1 wt-% Pt/Beta
and Pt/Y zeolites in the lean conditions with excess O2. The maximum conversion of NOx
was almost 70% over Pt/Beta and 60% over Pt/Y. NO started to react at above 150ºC over
all the catalysts except Pt/ZSM-5, which had the ignition temperature at 250ºC. In the
case when O2 was absent the NO conversion reached values of 71, 48, 59, and 98% over
 72
the 1 wt-% loaded Pt/ZSM-5, Pt/Beta, Pt/Y, and Pt/Ferrierite, respectively. The maximum
NO conversions were measured just above the temperature at which propene had reached
conversion of higher than 99% in the case of excess O2. In the absence of O2 the maxima
in the NO conversions were detected at the temperatures above 500°C, expect in the case
of the 1 wt-% Pt/Beta (390ºC). The activities of the catalysts for the reduction of NO
decreased in the order: Pt/Beta > Pt/Y > Pt/Ferrierite > Pt/ZSM-5 in the conditions with
excess O2.
The platinum loading can be observed to have a positive impact on catalyst efficiency
in oxidising hydrocarbons. The observed phenomenon can be concluded to be evidence
of the hydrocarbon cracking on the platinum surfaces. Further, the small hydrocarbon
species (CHx) formed can more efficiently react with the surface oxygen and/or NO
species. However, NO2 formation was observed to rise twofold in magnitude with all the
studied Pt-loaded catalysts compared to the parent zeolites. Platinum can be concluded to
have an effect on O2 and NO dissociation. Oxidation reactions of NO to NO2 and propene
to CO2 can be observed to be more intense over the platinum-loaded zeolites than over
the parent zeolites at lower temperatures.
The TPD studies of the adsorption of NO, propene as well as propene plus O2 on the
parent and Pt-loaded zeolite catalysts were done. The adsorption of NO indicates that NO
can be adsorbed on at least two different sites on the catalyst surface, except in the case
of Ferrierite-based catalysts. One adsorption site is concluded to be on the supporting
zeolite and the other site on Pt. Propene is detected to adsorb the strongest on the ZSM-5-
and Beta-based catalysts, while on the Y and Ferrierite zeolites propene adsorption is
almost negligible. With the inlet gas mixture of propene and O2 the Pt-ZSM-5 and Pt-
Beta zeolites showed major adsorption capacities. Propene adsorption was observed to
decrease in the following order: Pt/ZSM-5 > Pt/Beta >> Beta > ZSM-5 > Ferrierite ≈
Pt/Ferrierite > Pt/Y zeolite > Y zeolite.
The acidities of the parent and Pt-loaded zeolite catalysts show that pyridine was
adsorbed on the ZSM-5-based catalysts via the most irreversible bonds. The adsorption of
pyridine on the Brønsted and Lewis acid sites can be observed over all the catalysts
studied. The acidity was determined to decrease in the following order: Pt/ZSM-5 ≈
ZSM-5 > Pt/Beta ≈ Beta > Pt/Y > Y zeolite. The acidic properties of the parent and
Pt/loaded Ferrierite were not determined.
The average activation energies for NO reduction and propene oxidation were
calculated. The activation energies for NO reduction decreased in the following order:
Pt/Ferrierite > Pt/Y > Pt/Beta ≈ Pt/ZSM-5 and for propene oxidation the activation
energies decreased in the order: Pt-ZSM/5 > Pt/Ferrierite > Pt/Y ≈ Pt/Beta.
The comparison of the activity studies, adsorption properties and acidities of the
zeolite catalysts gives a guideline for the interaction of acidic surface sites and the
behaviour of catalysts in the reduction of NO in excess oxygen. It is significant that the
most acidic zeolites (ZSM-5 and Pt/ZSM-5) did not show the best activities for the NO
reduction or propene oxidation in excess O2. In addition, zeolite Y and Pt/Y omit good
activities for the HC-SCR of NO, though their acidities and adsorption capacities were
observed to be almost negligible.
The reaction mechanisms over the 1 wt-% Pt-loaded zeolite catalysts and the
Pd/Al2O3-based catalysts are found to have differences in the formation of reaction
intermediates. Over the Pd/Al2O3-based catalysts the main intermediates observed were
 73
nitrates, nitrites, isocyanates and formates, while various organonitrogen species were
considered to be formed as intermediates over the Pt-loaded zeolite catalysts. Over the Pt-
loaded zeolite catalysts the main reaction intermediates on the surface are concluded to
be organonitrogen species such as CXHY-NO2 and CXHY-ONO. The plausible reaction
mechanism has been derived and the NO oxidation to NO2 has been considered to be one
of the crucial mechanistic steps for the formation of organonitrogen species. These
species can further react with NO to desired products (N2, CO2, and H2O). However, the
well-known disadvantage of the Pt-loaded catalyst is the formation of N2O at the light-off
temperature. The formation of dinitrogen containing species on zeolite catalysts as
intermediates has also been reported in the literature. These species were, however, not
identified.
Palladium loaded Al2O3 catalysts have been studied widely and several reaction
mechanisms have been proposed in the literature. In this study, the Pd-loaded catalyst
was used as a reference for the mechanistic studies because of the detailed information in
the literature and our own earlier research and experience as well. The formation of
nitrates, nitrites, formates, acetates, and isocyanates was observed by the DRIFT
technique in the reduction of NO by propene over the Pd/Al2O3-based catalysts. The
reaction mechanism of HC-SCR of NO is proposed to go via these intermediates over the
Pd/Al2O3 catalysts. Our experimental studies of NO reduction by propene and CO over
Pd-loaded Al2O3-based catalysts also give convincing evidence of the reaction
mechanism that goes via -NCO and partially oxidised hydrocarbon species formation.
The DRIFT technique together with activity experiments is found to be a useful and
effective tool for the derivation of the reaction mechanism. The techniques used allow for
the detection of the main differences between the adsorbed surface species and the
possible intermediates formation over Pt-loaded zeolite and the Pd-loaded Al2O3-based
catalysts. In addition, while the determination of the surface species on the zeolite-based
materials is more difficult than on the alumina-based materials, the DRIFT technique was
proved to be a reliable research method in the case of zeolite materials as well.
Furthermore, the experimental data obtained by DRIFT and activity experiments can be
used to derive the kinetic model for the NO reduction by propene.
The reaction mechanisms of the HC-SCR of NOX over supported noble metal catalysts
are, however, very complicated and deriving a simple kinetic model that could describe
the phenomena on the catalysts surfaces with sufficient precision is very demanding and
even impossible. Thus, transient and isotopic labelling experiments can provide further
support to discriminate between the importance of the mechanistic steps inside each
mechanism proposed and also when comparing the different mechanisms. This could
very much facilitate the kinetic modelling.
 8 Conclusions
In this study the parent and 1 wt-% Pt/zeolite and the 1 wt-% Pd/Al2O3-based catalysts
were studied in the NO reduction by hydrocarbon and CO. The Pd-based catalyst has
been used as a reference material for Pt-loaded zeolite catalysts because the examination
of the zeolite materials is more demanding than that of alumina-based materials. The
main goal of the work was to gain new knowledge on the mechanisms of NO reduction
by propene over Pt-loaded zeolite catalysts. The second target was to study the IR
techniques and their applicability and reliability for investigating and identifying the
intermediates and adsorbed surface species in heterogeneous catalysis. The third goal was
to derive the reaction mechanism for NO reduction by propene in excess oxygen by using
only a few present-day experimental techniques and data from recent supporting
literature. Finally, the derived reaction mechanistic routes for propene-assisted NO
reduction over Pt/zeolites and Pd/Al2O3-based catalysts were compared.
Platinum-loaded zeolite catalysts are observed to oxidise hydrocarbons to CO2 as well
as NO to NO2 much more effectively than the parent zeolites. It can be concluded that
hydrocarbons are activated by platinum, and small reactive hydrocarbon species (CxHy)
are formed. These hydrocarbon species can be oxidised more efficiently with surface
oxygen and/or nitric oxide. The platinum loading is also detected to have a significant
effect on the catalyst activity by lowering the light-off temperature (T50) of propene and,
furthermore, the conversions of NO reach the maximum values at lower temperatures
than with the parent zeolites.
The excess oxygen in the inlet gas mixture is observed to lower the light-off
temperature of the catalysts. Propene reached over 99% conversion with all the Pt-loaded
catalysts. In addition, the maxima at the conversions of NO were reached at lower
temperatures. However, the conversions were smaller than with the inlet gas mixture of
NO+C3H6.
Another goal was to study the applicability of the IR techniques. The techniques were
found to be valid tools providing a good basis for the mechanistic evaluation and,
furthermore, for the creation of the kinetic models for the HC-SCR reactions of NO. The
DRIFT spectra of the intermediates and the adsorbed surface compounds under the
reaction provide a clear difference on the reaction intermediates over the Pt-loaded
 75
zeolites and Pd/Al2O3-based catalysts. Activity studies also give the guidelines for the
catalysts’ functioning in the reduction of NO by propene over the catalysts examined.
The comparison of the DRIFT spectra of the Pt-loaded zeolite and Pd/Al2O3-based
catalysts offers significant evidence of different reaction intermediates on the catalyst
surface during the two cases. Over the Pd/Al2O3-based catalysts the NO reduction was
concluded to go via isocyanates, nitrates and partially oxidised hydrocarbon
intermediates formation. In the case of the 1 wt-% Pt/zeolite catalysts the isocyanate
formation was not detected. However, the formation of organonitro species was observed.
Thus, the reaction mechanisms of NO reduction by propene over Pt/zeolites and
Pd/Al2O3-based catalysts can be concluded to be dissimilar based on the experimental
results obtained by DRIFT.
The most effective catalysts for the NO reduction by propene were found to be the 1
wt-% Pt/Beta and Pt/Y zeolite catalysts. However, the temperature windows for the
maximum reduction were observed to be quite narrow, smaller than 50ºC. It can be
concluded that the Pt-loaded zeolite catalysts are good materials for the C3H6-assisted
SCR of NO in the conditions studied. The reaction mechanistic approaches give the bases
for the kinetic modelling that will be done in the future. Further studies will be performed
in kinetic modelling as well as in the use of isotope-labelled molecules for making more
detailed analyses of the mechanistic routes.
In this thesis, IR techniques have been used as a tool for deriving the reaction
mechanisms for the propene-assisted SCR of NO. The Pt-loaded zeolite catalysts were
found to be effective simultaneously in NO mitigation and propene oxidation. It can be
concluded that the IR techniques can be used to derive the precise reaction mechanistic
model. The adsorbed and formed surface species can be identified by DRIFT and the
reaction products can be measured by gas FTIR in activity tests. The possibility that with
only a small number of present-day experimental techniques, i.e. simultaneous DRIFT
and FTIR, catalytic properties can be studied and reliable reaction mechanisms can be
derived makes these techniques useful for reactor design. Kinetic modelling can,
however, be facilitated by e.g. transient experiments, which give evidence of the
importance of each mechanistic step and can thus make the simplifications in the kinetic
models easier. The reaction routes for the NO reduction over the Pt-loaded zeolite and
Pd/Al2O3-based catalysts were concluded to go mainly via the organonitrogen and
isocyanate intermediates formation, respectively.
 References
ACEA (2004) Waiting for Euro 5 and Euro 6. New emission standards for passenger cars, vans and
lorries. T&E, Europe’s voice for sustainable transport. Factsheet 3/2004. European Federation
for Transport and Environment. http://www.t-e.nu/docs/Factsheets/2004/
EURO5andEURO6Briefing.pdf (30.11.2004)
Acke F & Skoglundh M (1999) Zeolite supported Pt catalysts for reduction of NO under oxygen
excess: a comparison of C3H6, HNCO and NH3 as reducing agents. Applied Catalysis B:
Environmental 20: 235-242.
Acres GJK & Harrison B (2004) The development of catalysts for emission control from motor
vehicles: early research at Johnson Matthey. Topics in Catalysis 28(1-4): 3-11.
Amiridis MD, Mihut C, Maciejevski M & Baiker A (2004) The selective catalytic reduction of NO
by hydrocarbons over Pt- and Ir-based catalysts. Topics in Catalysis 28(1-4): 141-150.
Amiridis MD, Roberts KL & Pereira CJ (1997) The selective catalytic reduction of NO by
propylene over Pt supported on dealuminated Y zeolite. Applied Catalysis B: Environmental 14:
203-209.
Amiridis MD, Zhang T & Farrauto RJ (1996) Selective catalytic reduction of nitric oxide by
hydrocarbons. Applied Catalysis B: Environmental 10: 203-227.
Armaroli T, Bevilacqua M, Trombetta M, Gutièrrez Alejandre A, Ramirez J & Busca G (2001) An
FT-IR study of the adsorption of aromatic hydrocarbons and of 2,6-lutidine on H-FER and H-
ZSM-5 zeolites. Applied Catalysis A: General 220: 181-190.
Baerlocher Ch & McCusker LB (2000) Database of Zeolite Structures. http://www.iza-
structure.org/databases/ (5.8.2005)
Bamwenda GR, Ogata A, Obuchi A, Oi, J, Mizuno K & Skrzypek J (1995) Selective catalytic
reduction of nitric oxide with propene over platinum-group based catalysts: Studied of surface
species and catalytic activity. Applied Catalysis B: Environmental 6: 311-323.
Benitez JJ, Carrizosa I & Odriozola JA (1994). Diffuse reflectance FT-IR characterization of active
sites under reaction conditions: The production of oxygenates in the CO/H2 reaction. Applied
Spectroscopy 48 (10): 1208-1212.
Bludau H, Karge HG & Niessen W (1998) Sorption, sorption kinetics and diffusion of pyridine in
zeolites. Microporous and Mesoporous Materials 22: 297-308.
Bolis V, Vedrine JC, van den Berg JP, Wolthuizen JP & Derouane EG (1980) Adsorption and
activation of ethane by zeolite-H-ZSM-5. Journal of the Chemical Society Faraday Transaction I
76: 1606-1616.
 77
Bordiga S, Turnes Palomino G, Pazè C & Zecchina A (2000) Vibrational spectroscopy of H2, N2,
CO and No adsorbed on H, Li, Na, K-exchanged ferrierite. Microporous and Mesoporous
Materials 34: 67-80.
Bortnovsky O, Sobalík Z & Wichterlová B (2001) Exchange of Co(II) ions in H-BEA zeolites:
identification of aluminium pairs in the zeolite framework. Microporous and Mesoporous
Materials 46: 265-275.
Botas JA, Gutíerrez-Ortiz MA, González-Marcos MP, González-Marcos JA & González-Velasco
JR (2001) Kinetic considerations of three-way catalysis in automobile exhaust converters.
Applied Catalysis B. Environmental 32: 243-256.
Brosius R & Martens JA (2004) Reaction mechanisms of lean-burn hydrocarbon SCR over zeolite
catalysts. Topics in Catalysis 28(1-4): 119-130.
Bueno-López A, Illán-Gómez MJ & Salinas-Martínez de Lecea C (2006) Effect of NOx and C3H6
partial pressures on the activity pf Pt-Beta-coated cordierite monolitos for deNOx C3H6-SCR.
Applied Catalysis A: General 302: 244-249.
Bueno-López A, Lozano-Castelló D, Such-Basáñez I, Carcía-Cortés JM, Illán-Gómez MJ &
Salinas-Martínez de Lecea C (2004) Preparation of beta-coated cordierite honeycomb monoliths
by in situ synthesis. Utilisation as Pt support for NOx abatement in diesel exhaust. Applied
Catalysis B: Environmental 58: 1-7.
Burch R (2004) Knowledge and know-how in emission control for mobile applications. Catalysis
Reviews 46(3-4): 271-333.
Burch R, Breen JP & Meunier FC (2002) A review of the selective reduction of NOx with
hydrocarbons under lean-burn conditions with non-zeolitic oxide and platinum group metal
catalysts. Applied Catalysis B: Environmental 39: 283-303.
Burch R & Scire S (1994a) An investigation of the mechanism of the selective catalytic reduction
of NO on various metal/ZSM-5 catalysts: reactions of H2/NO mixtures. Catalysis Letters 27:
177-186.
Burch R & Scire S (1994b) Selective catalytic reduction of nitric oxide with ethane and methane on
some metal exchanged ZSM-5 zeolites. Applied Catalysis B: Environmental 3: 295-318.
Burch R & Watling TC (1997) Kinetics and mechanism of the reduction of NO by C3H8 over
Pt/Al2O3 under lean-burn conditions. Journal of Catalysis 169: 45-54.
Burch R & Watling TC (1998) The effect of sulphur on the reduction of NO by C3H6 and C3H8
over Pt/Al2O3 under lean-burn conditions. Applied Catalysis B: Environmental 17: 131-139.
Cant NW & Liu IOY (2000) The mechanism of the selective reduction of nitrogen oxides by
hydrocarbons on zeolite catalysts. Catalysis Today 63: 133-146.
Captain DK, Roberts KL & Amiridis MD (1998) The selective reduction of nitric oxide by
propylene over Pt/SiO2. Catalysis Today 42: 93-100.
Chen H-H, Shen S-C, Chen X & Kawi S (2004) Selective catalytic reduction of NO over Co/beta-
zeolite: effects of synthesis condition of beta-zeolites, Co precursor, Co loading method and
reductant. Applied Catalysis B: Environmental 50: 37-47.
Cho BK & Yie JE (1996) Nitric oxide reduction by ethylene over Pt-ZSM-5 under lean conditions:
steady-state activity. Applied Catalysis B: Environmental 10: 263-280.
Cho BK, Yie JE & Rahmoeller KM (1995) Autonomous kinetic oscillations during NO + C2H4 +
O2 reaction over Pt-ZSM-5 under highly oxidising conditions. Journal of Catalysis 157: 14-24.
Ciambelli P, Corbo P, Gaudino MC, Migliardini F & Sannino D (2001) Investigation of Co-based
deNOx catalysts for the treatment of natural gas lean-burn engine exhaust. Topics in Catalysis
16/17(1-4): 413-417.
Corma A (1995) Inorganic solid acids and their use in acid-catalyzed hydrocarbon reactions.
Chemical Reviews 95: 559-614.
Corma A, Fornés V & Palomares E (1997) Selective catalytic reduction of NOx on Cu-beta
zeolites. Applied Catalysis B: Environmental 11: 233-242.
 78
Cowan AD, Cant NW, Haynes BS & Nelson PF (1998) The catalytic chemistry of nitromethane
over Co-ZSM-5 and other catalysts in connection with the methane-NOxSCR reaction. Journal
of Catalysis 176: 329-343.
Dai P-SE (1995) Zeolite catalysis foa a better environment. Catalysis Today 26: 3-11.
Dĕdeček J, Kaucký D & Wichterlová B (2002) Does density of cationic sites affect catalytic
activity of Co zeolites in selective catalytic reduction of NO with methane. Topics in Catalysis
18(3-4): 283-290.
Deeba M, Feeley J & Farrauto R (1999) Lean NOx: dual sites for NOx reduction on Pt/H-ZSM-5.
Applied Catalysis A: General 188: 219-227.
Delahay G & Coq B (2002) Chapter 16, Pollution abatement using zeolites: State of the art and
further needs. In: Guisnet M & Gilson J-P (eds.) Zeolites for cleaner technologies. Imperial
College Press, Singapore, 345-374.
Denton P, Giroir-Fendler A, Schuurman Y, Praliaud H. Mirodatos C & Primet M (2001) A redox
pathway for selective NOx reduction: stationary and transient experiments performed on a
asupported Pt catalyst. Applied Catalysis A: General 220: 141-152.
Dieselnet_EU (2005) Dieselnet: Emission standards: European Union. Cars and Light Truks.
http://www. dieselnet.com/standards/eu/ld.html (30.11.2005)
Dieselnet_USA (2004) Dieselnet: Emission standards: USA: Cars and Light Trucks. http://www.
dieselnet.com/standards/us/light.html (29.11.2005)
Duprat F (2002) Light-off curve of catalytic reaction and kinetics. Chemical Engineering Science
57: 901-911.
EPA (1999) US Environmental Protection Agency. Control of Diesel fuel quality. 40 CFR Parts 80
and 86 [AMS-FRL-6337-4] RIN 2060-AI32. Federal Register 64(92): 26142-26158.
http://www.epa.gov/fedrgstr/EPA-AIR/1999/May/Day-13/a11383.htm (2.8.2005)
EPA (2000) US Environmental Protection Agency. Federal Certification Exhaust Emission
Standards for Light-Duty Vehicles (Passenger Cars and Light Light-Duty Trucs: Federal Test
Procedure (FTP), Cold CO, and Highway & Idle Tests. EPA420-B-00-001. February 2000.
EPA (2002) US Environmental Protection Agency. Control of Air Pollution from New Motor
Vehicles: Amendments to the Tier 2 Motor Vehicle Emission Regulations. Federal Register
Environmental Documents 67(235): 72821-72826. http://www.epa.gov/fedrgstr/EPA-
AIR/2002/December/Day-06/a30843.htm (5.7.2005)
Ermini V, Finoccio E, Sechi S, Busca G & Rossini S (2000) An FT-IR and flow reactor study of
the conversion of propane on γ-Al2O3 in oxygen-containing atmosphere. Applied Catalysis A:
General 190: 157-167.
EU (1970) Directive 70/220/EEC EU Council Directive 70/220/EEC of 20 March 1970 on the
approximation of the laws of the Member States relating to measures to be taken against air
pollution by gases from positive-ignition engines of motor vehicles. Official Journal L 076,
06/04/1970 P. 1-22.
EU (1998) Directive 98/69/EC EU Council Directive 98/69/EC of 13 October 1998 relating to
measures to be taken against air pollution by emissions from motor vehicles and amending
Council Directive 70/220/EEC. Official Journal of the European Communities L
350.28/12/1998 P. 1-56.
EU (2005) Preliminary draft proposal for a Regulation of the European Parliament and of the
Council relating to emissions of atmospheric pollutants from motor vehicles (Euro 5). European
Commission services. http://europa.eu.int/comm/enterprise/automotive/pagesbackground/
pollutant_emission/stakeholder_consultation/euro_5_draft_reg.pdf (11.8.2005)
Falconer JL & Schwarz JA (1983) Temperature-programmed desorption and reaction: Application
to supported catalysts. Catalysis Reviews – Science and Engineering 25(2): 141-227.
Fritz A & Pitchon V (1997). The current state of research on automotive lean NOx catalysis
Applied Catalysis B: Environmental 13: 1-25.
 79
Furusawa T, Seshan K. Leffers L & Aika K-i (2002) Selective reduction of NO with prolylene in
the presence of oxygen over Co- and Pt-Co promoted HY. Applied Catalysis B: Environmental
39: 233-246.
Gabrielsson PLT (2004) Urea-SCR in automotive applications. Topics in Catalysis 28(1-4): 177-
184.
García-Cortéz JM, Pérez-Ramírez J, Illán-Gómez MJ & Salinas-Martínez de Lecea C (2003a)
Activation by sintering of Pt-Beta catalysts in deNOx HC-SCR. Structure-activity relationships.
Catalysis Communications 4: 165-170.
García-Cortéz JM, Pérez-Ramírez J, Rouzaud JN, Vaccaro, AR, Illán-Gómez MJ & Salinas-
Martínez de Lecea C (2003b) On the structure sensitivity of deNOx HC-SCR over Pt-beta
catalysts. Journal of Catalysis 218: 111-122.
Gerlach T, Schütze F-W & Baerns M (1999a) An FTIR study on the mechanism of the reaction
between nitrogen dioxide and propene over acidic mordenites. Journal of Catalysis 185: 131-
137.
Gerlach T, Illgen U, Bartoszek M & Baerns M (1999b) Reduction of nitrogen dioxide by propene
over acidic mordenites: influence of acid site concentration, formation of by-products and
mechanism. Applied Catalysis B: Environmental 22: 269-278.
Gilot P, Guyon M & Stanmore BR (1997) A review of NOx reduction on zeolitic catalysts under
diesel exhaust conditions. Fuel 76: 507-515.
Giroir-Fendler A, Denton P, Boreave A, Praliaud H & Primet M (2001) The role of support acidity
in the selective catalytic reduction of NO by C3H6 under lean-burn conditions. Topics in
Catalysis 16/17(1-4): 237-241.
Glick HS, Klien JJ & Squire W (1957) Single-pulse shoct tube studies if the kinetics of the reaction
N2+O2⇄2NO between 2000-3000ºK. The Journal of Chemical Physics 27(4): 850-857.
Gregg SJ & Sing KSW (1982) Adsorption, surface area and porosity. 2nd ed. Academic Press,
London, 303.
Guisnet M & Gilson J-P (2002) Chapter 1. Introduction to zeolite science and technology. In:
Guisnet M & Gilson J-P (eds) Zeolites for cleaner technologies. Catalytic Science Series – Vol.
3. Imperial College Press, Singapore, 1-28.
Guo J, Konno M, Chikahisa T, Murayama T & Iwamoto M (1995) NOx reduction characteristics of
Pt-ZSM-5 catalyst with diesel engine exhaust. JSAE Review 16: 21-25.
Haagen-Smit AJ (1952) Chemistry and physiology of Los Angeles smog. Industrial and
Engineering Chemistry 44(6): 1342-1346.
Haagen-Smit AJ & Fox MM (1956) Ozone formation in photochemical oxidation of organic
substances. Industrial and Engineering Chemistry 48(9): 1484-1487.
Hadjiivanov K, Tsyntsarski B & Nikovola T (1999) Stability and reactivity of the nitrogen-oxo
species formed after NO adsorption and NO+O2 coadsorption on Co-ZSM-5: An FTIR
spectroscopic study. Physical Chemistry Chemical Physics 2: 4521-4528.
Halász J, Imre B & Hannus I (2004) IR spectroscopic investigation of hydrodechlorination on Pt-
containing zeolites. Applied Catalysis A: General 271: 47-53.
Hamada H (1997) Cooperation of catalytic species for the selective reduction of nitrogen monoxide
with hydrocarbons. Catalysis surveys from Japan 1: 53-60.
Harmsen JMA, Hoebink JHBJ & Schouten JC (2001) Acetylene and carbon monoxide oxidation
over a Pt/Rh/CeO2/γ-Al2O3 automotive exhaust gas catalyst: kinetic modeling of transient
experiments. Chemical Engineering Science 56: 2019-2035.
Heck R & Farrauto R (1997) The automobile catalyst. Its present and future family tree. CatTech
1(2): 117-124.
Heck R & Farrauto R (2001) Automobile exhaust catalysts. Applied Catalysis A: General 221: 443-
457
 80
Hindmarsh AC (1980) LSODE and LSODI, Two new initial value ordinary differential equation
solvers. ACM SIGNUM Newsletter 15: 10-11
Ho L-W, Hwang C-P, Lee J-F, Wang I & Yeh C-T (1998) Reduction of platinum dispersed on
dealuminated beta zeolite. Journal of Molecular Catalysis A: Chemical 136: 293-299.
Holma T, Palmqvist A, Skoglundh M & Jobson E (2004) Applied Catalysis B: Environmental 48:
95-100.
Hoost TE, Laframboise KA & Otto K (1995a) Co-adsorption of propene and nitrogen oxides on
Cu-ZSM-5: An FTIR study. Applied Catalysis B: Environmental 7: 79-93.
Hoost TE, Otto K & Laframboise KA (1995b) FTIR spectroscopy of nitric oxide adsorption on
Pd/Al2O3: Evidence of metal-support interaction. Journal of Catalysis 155: 303-311.
Hybrid Cars (2005) Hybrid Cars - Emission Standards. http://www.hybridcars.com/emissions.html.
(5.7.2005).
Ingelsten HH, Hildesson Å, Fridell E & Skoglundh M (2004) The influence of surface acidity in
NO2 reduction by propane under lean conditions. Journal of Molecular Catalysis A: Chemical
209: 199-207.
Intriago L, Díaz E, Ordóñez S & Vega A (2006) Combustion of trichloroethylene and
dichloromethane over protonic zeolites: Influence of adsorption properties on the catalytic
performance. Microporous and Mesoporous Materials 91: 161-169.
Ioan B, Miyazaki A & Aika K-I (2005) On the kinetic and structure sensitivity of lean reduction of
NO with C3H6 over nanodispersed Pt crystals. Applied Catalysis B: Environmental 59: 71-80.
Iojoiu E, Gélin P, Praliaud H and Primet M (2004) Reduction of NO by propene over supported
iridium catalysts under lean-burn conditions: a in situ FTIR study. Applied Catalysis A: General
263: 39-48.
Iwamoto M, Yahiro H, Shin HK, Watanabe M, Guo J, Konno M, Chikahisa T & Murayama T
(1994) Performance and durability of Pt-ZSM-5 zeolite catalyst fpr selective reduction of
nitrogen monoxide in actual diesel engine exhaust. Applied Catalysis B: Environmental 5: L1-
L5.
Janin A, Maache M, Lavalley JC, Joly JF, Raatz F & Szydlowski N (1991) FT i.r. study of the
silanol groups in dealuminated HY zeolites: Nature of the extraframework depris. Zeolites 11:
391-396.
Kamijo M, Kamikubo M, Akama H & Matsushita K (2001) Study of an oxidation catalyst system
for diesel emission control utilizing HC adsorption. JSAE Review 22: 277-280
Kašpar J, Fornasiero P & Hickey N (2003) Automotive catalytic converters: current status and
some perspectives. Catalysis Today 77: 419-449.
Keiski RL, Härkönen M, Lahti A, Maunula T, Savimäki A & Slotte T (1995) An infrared study of
CO and NO adsorption on Pt, Rh, Pd 3-way catalysts. Studies in Surface Science and Catalysis,
vol 96. In: Frennet A & Bastin J-M (eds) Catalysis and Automotive Pollution Control III.
Elsevier. Amsterdam. 85-96.
Keiski RL, Räisänen H, Härkönen M, Maunula T & Niemistö P (1996) NOx abatement in lean
exhaust gas conditions over metal substrated zeolite catalysts. Catalysis Today 27: 85-90.
Kinger G, & Vinek H (2001) n-Nonane hydroconversion on NiO and Pt containing HMFI, HMOR
and HBEA. Applied Catalysis B: Environmental 218: 139-149.
Kolli T, Rahkamaa-Tolonen K, Lassi U, Savimäki A & Keiski RL (2005) Influence of BaO on
Pd/Al2O3 based catalysts in C2H4 and CO oxidation as well as in NO reduction. Catalysis Today
100: 303-307.
Krishna K, Seijger GBF, van den Bleek CM, van Bekkum H & Calis HPA (2002) Selective
catalytic reduction of NOx with propene over CeO2-ferrierite. Chemical Communications (9):
948-949.
König A, Held W & Richter T (2004) Lean-burn catalysts from the perspective of a car
manufacturer. Early work at Volkswagen Research. Topics in Catalysis 28(1-4): 99-103.
 81
Lassi U. (2003) Deactivation correlations of Pd/Rh three-way catalysts designed for EURO IV
emission limits. Doctoral Thesis, University of Oulu, Oulu, Finland.
Li G, Larsen SC & Grassian VH (2005) Catalytic reduction of NO2 in nanocrystalline NaY zeolite.
Journal of Molecular Catalysis A: Chemical 227: 25-35.
Li Y & Armor JN (1994) Catalytic combustion of methane over palladium exchanged zeolites.
Applied Catalysis B: Environmental 3: 275-282.
Maache M, Janin A, Lavalley JC, Joly JF & Benazzi E (1993) Acidity of zeolites Beta
dealuminated by acid leaching: An FTi.r. stusy using different probe molecules (pyridine,
carbon monoxide). Zeolites 13: 419-426.
Machida M & Watanabe T (2004) Effect of Na-addition on catalytic activity of Pt-ZSM-5 for low-
temperature NO-H2-O2 reactions. Applied Catalysis B: Environmental. 52: 281-286.
Macleod N, Isaac J & Lambert RM (2001) Sodium promotion of Pd/γ-Al2O3 catalysts operated
under simulated “Three-Way” conditions. Journal of Catalysis 198: 128-135.
Maisuls SE, Lefferts L, Seshan K, Furusawa T, Aika K, Mosqueda-Jimenez B, Smidt M & Lercher
JA (2003) Selective catalytic reduction of NO with propylene in the presence of oxygen over
Co-Pt promoted H-MFI and HY. Catalysis Today 84: 139-147.
Martens JA, Cauvel A, Jayat F, Vergne S & Jobson E (2001) Molecule sieving catalysts for NO
reduction with hydrocarbons in exhaust of lean burn gasoline and diesel engines. Applied
Catalysis B: Environmental 29: 299-306.
Martin A, Wolf U, Nowak S & Lücke B (1991) Pyridine-i.r. investigations of hydrothermally
treated dealuminated HZSM-5 zeolites. Zeolites 11: 85-87.
Marquardt DW (1963) An algorithm for least-squares estimation of nonlinear parameters. Journal
of the Society for Industrial and Applied Mathematics 11(29): 431-441.
Massing E, Brilhac JF, Brillard A, Gilot P & Prado G (2000) Modelling of the behaviour of a three
way catalytic converter at steady state; Influence of the propene diffusion inside the catalytic
layer. Chemical Engineering Science 55: 1707-1716.
Maunula T, Ahola J & Hamada H (2000) Reaction mechanism and kinetics of NOx reduction by
propene on CoOx/alumina catalysts in lean conditions. Applied Catalysis B: Environmental 26:
173-192.
Meunier FC, Breen JP, Zuzaniuk V, Olsson M & Ross JRH (1999) Mechanistic aspects of the
selective catalytic reduction of NO by propene over alumina and silver-alumina catalysts.
Journal of Catalysis 187: 493-505.
Mihaylov M, Hadjiivanov K & Panayotov D (2004) FTIR mechanistic studies on the selective
catalytic reduction of NOx with methane over Ni-containing zeolites: comparison between NiY
and Ni-ZSM-5. Applied Catalysis B: Environmental 51: 33-42.
Monnerat B, Kiwi-Minsker L & Renken A (2003) Mathematical modelling of the unsteady-state
oxidation of nickel gauze catalysts. Chemical Engineering Science 58: 4911-4919.
Mukadi LS & Hayes RE (2002) Modelling the three-way catalytic converter with mechanistic
kinetics using the Newton-Krylov method on a parallel computer. Computers and Chemical
Engineering 26: 439-455.
Nakatsuji T, Shimizu H, Yasukawa R, Kawatsuki M, Tabata M, Tsuchida H, Kintaichi Y & Sasaki
M (1995) Catalyst for catalytic reduction of nitrogen oxide. US Patent 5 474 965, assigned to
Sakai Chemical Industry Corporation, Petroleum Energy Center, Cosmo Oil Corporation and
Agency of Industrial Science and Technology.
Nelder JA & Mead RA (1965) A simplex method for function minimization. Computer Journal 7:
308-313.
Nikolopoulos AA, Stergioula ES, Efthimiadis EA & Vasalos IA (1999) Selective catalytic
reduction of NO by propene in excess oxygen on Pt- and Rh-supported alumina catalysts.
Catalysis Today 54: 439-450.
 82
Obuchi A, Kaneko I, Oi J, Ohi A, Ogata A, Bamwenda G.R & Kushiyama S (1998) A practical
scale evaluation of catalysts for the selective reduction of NOx with organic substances using a
diesel exhaust. Applied Catalysis B: Environmental 15: 37-47.
Oh SH, Fisher GB, Carpenter JE & Goodman DW (1986) Comparative kinetic studies of CO-O2
and CO-NO reactions over single crystal and supported rhodium catalysts. Journal of Catalysis
100: 360-376.
Parker LM, Bibby DM & Burns GR (1993) An infrared study of H2O and D2O on HZSM-5 and
DZSM-5. Zeolites 13: 107-112.
Pârvulescu VI, Grange P & Delmon (1998) Catalytic removal of NO. Catalysis Today 46: 233-316.
Pérez-Ramírez J, Carcía-Cortéz JM, Kapteijn F, Mul G, Moulijn JA & Salinas-Martínez de Lecea
C (2001) Characterization and performance of Pt-USY in the SCR of NOx with hydrocarbons
under lean-burn conditions. Applied Catalysis B: Environmental 29: 285-298.
Petersson M, Holma T, Andersson B, Jobson E & Palmqvist A (2005) Lean hydrocarbon selective
catalytic reduction over dual pore system zeolite mixtures. Journal of Catalysis 235: 114-127.
Petunchi JO & Hall WK (1994) Effect of selective reduction of nitric oxide on zeolite structure.
Applied Catalysis B: Environmental 3: 239-257.
Poignant F, Freysz JL, Daturi M & Saussey J (2001) Mechanism of the selective catalytic reduction
of NO in oxygen excess by propane on H-Cu-ZSM-5. Formation of isocyanide species via
acrylonitrile intermediate. Catalysis Today 70: 197-211.
Pontikakis GN, Koltsakis GC, Stamatelos AM, Noirot R, Agliany Y, Colas H, Versaevel P &
Bourgeois C (2001) Experimental and modeling study on zeolite catalysts for diesel engines.
Topics in Catalysis 16/17: 329-335.
Praserthdam P, Chaisuk C, Panit A & Kraiwattanawong K (2002) Some aspects about the nature of
surface species on Pt-based and MFI-based catalysts for the selective catalytic reduction of NO
by propene under lean-burn condition. Applied Catalysis B: Environmental 38: 227-241.
Radtke F, Koeppel RA, Minardi EG & Baiker A (1997) Catalytic reduction of nitrogen oxides by
olefins in the presence of oxygen over copper/alumina: Influence of copper loading and
formation of byproducts. Journal of Catalysis 167: 127-141.
Radziszewski JG Downing JW, Gudipati MS, Balaji V, Thulstrup EW & Michl J (1996) How
predictable are IR transition moment directions? Vibrational transitions in propene and
deuterated propenes. Journal of American Chemical Society 118: 10275-10284.
Rahkamaa-Tolonen K, Maunula T, Lomma M, Huuhtanen M & Keiski RL (2005) The effect of
NO2 on the activity of fresh and aged zeolite catalysts in the NH3-SCR reaction. Catalysis
Today 100: 217-222.
Ribeiro FR (1984) Use of platinum HY zeolite and platinum H mordenite in the hydroisomerization
of n-hexane. In: Ribeiro FR, Rodrigues AE, Rollmann LD & Naccache C (eds) Zeolites:
Science and technology. NATO ASI Series E: Applied Sciences - No 80. Martinus Nijhoff
Publishers, The Hague, 545-569.
Roberts KL & Amiridis MD (1997) Kinetic investigation of the selective catalytic reduction of
nitric oxide propylene over Pt/Al2O3. Industrial Engineering & Chemical Research 36: 3528-
3532.
Roduit B, Baiker A, Bettoni F, Baldyga J & Wokaun A (1998) 3-D modeling of SCR of NOx by
NH3 on vanadia honeycomb catalysts. AiChE Journal 44(12): 2731-2744.
Rottländer C, Andorf R, Plog C, Krutzsch B & Baerns M (1996) Selective NO reduction by
propane and propene over a Pt/ZSM-5 catalyst: a transient study of the reaction mechanism.
Applied Catalysis B: Environmental 11: 49-63.
Sakamoto E, Ohnishi T, Okukawa A & Arakawa T (1997) Catalytic reduction of nitric oxide with
propane over Pt-T (T: transition metal) ion exchanged mordenites. Applied Surface Science
121/122: 421-424.
 83
Satsuma A, Hashimoto M, Shibata J, Yoshida H & Hattori T (2003) Nitrous oxide free pathways
for selective reduction of NO by hydrogen over supported Pt catalysts. Chemical
Communications 14: 1698-1699.
Schmieg SJ, Cho BK & Oh SH (2004) Selective catalytic reduction of nitric oxide with
acetaldehyde over NaY zeolite catalyst in lean exhaust feed. Applied Catalysis B:
Environmental 49: 113-125.
Shen S-C & Kawi S (2003) Selective catalytic reduction of NO by hydrocarbons in the presence of
excess oxygen using Pt/MCM-41 catalysts. Applied Catalysis B: Environmental 45: 63-76.
Shimizu K-i, Kawabata H, Satsuma A & Hattori T (1998) Formation and reaction of surface acetate
on Al2O3 during NO reduction by C3H6. Applied Catalysis B 19: L87-L92.
Shimizu K-i, Kawabata H, Satsuma A & Hattori T (1999) Role of acetate and nitrates in the
selective catalytic reduction of NO by propene over alumina catalysts as investigated bt FTIR.
Journal of Physical Chemistry 103: 5240-5245.
Shin HK, Hirabayashi H, Yahiro H, Watanabe M & Iwamoto M (1995) Selective catalytic
reduction of NO by ethane in excess oxygen over platinum ion-exchanged MFI zeolites.
Catalysis Today 26: 13-21.
SigmaPlot (2002) SigmaPlot 9.0 Tutorial. Systat Software Inc. SPSS Inc.
Sjövall H, Olsson L, Fridell E & Blint RJ (2006) Selective catalytic reduction of NOx with NH3
over Cu-ZSM-5 – The effect of changing the gas composition. Applied Catalysis B:
Environmental 64: 180-188.
Skoglundh M & Fridell E (2004) Strategies for enhancing low-temperature activity. Topics in
Catalysis 28(1-4): 79-87.
Sirilumpen M, Yang RT & Tharapiwattananon N (1999) Selective catalytic reduction of NO with
hydrocarbon on Cu2+-exchanged pillared clay: An IR study of the NO decomposition
mechanism. Journal of Molecular Catalysis A: Chemical 137: 273-286.
Sullivan JA, Cunningham J, Morris MA & Keneavey K (1995) Conditions in which Cu-ZSM-5
outperforms supported vanadia catalysts in SCR of NOx by NH3. Applied Catalysis B:
Environmental 7: 137-151.
Tabata T, Ohtsuka H, Sabatino LMF & Bellussi G (1998) Selective catalytic reduction of NOx by
propane on Co-loaded zeolites. Microporous and Mesoporous Materials 21: 517-524.
Tabata M, Tsuchida H, Miyamoto K, Yoshinari T, Yamazaki H, Hamada H, Kintaichi Y, Sasak, M
& Ito T (1995) Reduction of NOx in diesel exhaust with methanol over alumina catalyst.
Applied Catalysis B: Environmental. 6: 169-183.
Takami A, Takemoto T, Iwakuni H, Yamada K, Shigetsu M & Komatsu K (1997) Zeolite-
supported precious metal catalysts for NOx reduction in lean burn engine exhaust. Catalysis
Today 35: 75-81.
Tanabe T, Hatanaka M. Tsuji R & Shinjoh H (2002) NOx selective catalytic reduction over Pt
supported catalyst promoted by zeolite and CeO2-ZrO2. R&D Review of Toyota CRDL 37(3):
25-31.
Tanaka T, Okuhara T & Misono M (1994) Intermediacy of organic nitro and nitrite surface species
in selective catalytic reduction of nitrogen monoxide by propene in the presence of excess
oxygen over silica-supported platinum. Applied Catalysis B 4: L1-L9.
TEMET (2000) Instruction Manual for GASMET™. TEMET Instruments Oy. 31.
Terada K, Narishige T, Nakanishi Y & Fukuda K (1997) Exhaust emission control catalyst.
European Patent Application 801 972, assigned to Honda Giken Kogyo Kabushiki Kaisha.
Topsøe N-Y (1997) Catalysis for NOx abatement. Selective catalytic reduction of NOx by
ammonia: fundamental and industrial aspects. CatTech 1(2): 125-134.
Traa Y, Burger B & Weitkamp J (1999) Zeolite-based materials for the selective catalytic reduction
of NOx with hydrocarbons. Microporous and Mesoporous Materials 30: 3-41.
 84
UMIST Centre for Microporous Materials, web-site. http://www.umist.ac.uk/departments/
chemistry/cmm/ jonathansci.htm. (20.10.2004).
Villegas JI, Kumar N, Heikkilä T, Smiešková, Hudec P, Salmi T & Murzin DY (2005) A highly
stable and selective Pt-modified mordenite catalyst for the skeleteal isomerization of n-butane.
Applied Catalysis A: General 284: 223-230.
Walsh MP (1999) Motor vehicle standards and regulations around the world. Arlington, USA. 124.
Wang A, Ma L, Cong Y. Zhang T & Liang D (2003) Unique properties of Ir/ZSM-5 catalyst for
NO reduction with CO in the presence of excess oxygen. Applied Catalysis B: Environmental
40: 319-329.
Webb PA & Orr C (1997) Analytical methods in fine particle technology. Micromeritics Instrument
Corporation, Norcross, USA. 53-153.
Wichterlová B (2004) Structuraql analysis of potential active sites in metallo-zeolites for selective
catalytic reduction of NOx. An attempt for the structure versus activity relationship. Topics in
Catalysis. 28(1-4): 131-140.
Wojciechowska M & Lomnicki S (1999) Nitrogen oxides removal by catalytic methods. Clean
Products and Processes 1: 237-247.
Wögerbauer C, Maciejewski M, Baiker A & Göbel U (2001) Ir/H-ZSM-5 catalysts in the selective
reduction of NOx with hydrocarbons. Topics in Catalysis 16/17(1-4): 181-186.
Yokota K, Fukui M & Tanaka T (1997) Catalytic removal of nitric oxide with hydrogen and carbon
monoxide in the presence of excess oxygen. Applied Surface Science 121/122: 273-277.
Xin M, Hwang IC & Woo SI (1997a) In situ FTIR study of the selective catalytic reduction of NO
over Pt/ZSM-5. Catalysis Today 38: 187-192.
Xin M, Hwang IC & Woo SI (1997b) FTIR studies of the reduction of nitric oxide by propene on
Pt/ZSM-5 in the presence of oxygen. Journal of Physical Chemistry B. 101: 9005-9009.
Xu L, McCabe RW & Hammerle RH (2002) NOx self-inhibition in selective catalytic reduction
with urea (ammonia) over a Cu-zeolite catalyst in diesel exhaust. Applied Catalysis B:
Environmental. 39: 51-63.
Zeolyst Intenational (1999) web-site. http://www.zeolyst.com/html/faq.html (20.10.2004)
Zheng J, Song C, Xu X, Turaga T & Zhao XS (2004) Chapter 15: Acidity measurement of
nanoporous aluminosilicates – zeolites and MCM-41. In: Lu GQ (ed.) Nanoporous materials:
Science and engineering. Imperial College Press, London, 473-486.
 List of original papers

I Huuhtanen M, Määttä T, Rahkamaa-Tolonen K, Maunula T & Keiski RL (2004)

Adsorption of propene in the presence and absence of oxygen or nitric oxide on Pt-
loaded ZSM-5, Beta, Y and Ferrierite zeolites. Topics in Catalysis 30/31: 359-363.
II Huuhtanen M, Rahkamaa-Tolonen K, Maunula T & Keiski RL (2005) Pt-loaded
zeolites for reducing exhaust gas emissions at low temperatures and in lean
conditions. Catalysis Today 100(3-4): 321-325.
III Huuhtanen M, Maunula T & Keiski RL (2005) Reaction mechanism for C3H6-SCR
of NO over a Pt loaded ZSM-5 zeolite catalyst. Studies in Surface Science and
Catalysis 158: 1867-1874.
IV Ahola J, Huuhtanen M & Keiski RL (2003) Integration of in situ FTIR studies and
catalyst activity measurements in reaction kinetic analysis. Industrial Engineering &
Chemical Research 42(12): 2756-2766.
V Huuhtanen M, Kolli T, Maunula T & Keiski RL (2002) In situ FTIR study on NO
reduction by C3H6 over Pd-based catalysts. Catalysis Today 75(1-4): 379-384.
I Reprinted with kind permission from Springer Science and Business Media.
II, III and V Reprinted with permission from Elsevier.
IV Reproduced with permission from American Chemical Society. Copyright 2003.
Original publications are not included in the electronic version of the dissertation.
C261etukansi.fm Page 2 Tuesday, November 21, 2006 10:18 AM

ACTA UNIVERSITATIS OULUENSIS

SERIES C TECHNICA

243. Stoor, Tuomas (2006) Air in pulp and papermaking processes

244. György, Zsuzsanna (2006) Glycoside production by in vitro Rhodiola rosea
cultures
245. Özer-Kemppainen, Özlem (2006) Alternative housing environments for the
elderly in the information society. The Finnish experience
246. Laurinen, Perttu (2006) A top-down approach for creating and implementing data
mining solutions
247. Jortama, Timo (2006) A self-assessment based method for post-completion audits
in paper production line investment projects
248. Remes, Janne (2006) The development of laser chemical vapor deposition and
focused ion beam methods for prototype integrated circuit modification
249. Kinnunen, Matti (2006) Comparison of optical coherence tomography, the pulsed
photoacoustic technique, and the time-of-flight technique in glucose
measurements in vitro
250. Iskanius, Päivi (2006) An agile supply chain for a project-oriented steel product
network
251. Rantanen, Rami (2006) Modelling and control of cooking degree in conventional
and modified continuous pulping processes
252. Koskiaho, Jari (2006) Retention performance and hydraulic design of constructed
wetlands treating runoff waters from arable land
253. Koskinen, Miika (2006) Automatic assessment of functional suppression of the
central nervous system due to propofol anesthetic infusion. From EEG
phenomena to a quantitative index
254. Heino, Jyrki (2006) Harjavallan Suurteollisuuspuisto teollisen ekosysteemin
esimerkkinä kehitettäessä hiiliteräksen ympäristömyönteisyyttä
255. Gebus, Sébastien (2006) Knowledge-based decision support systems for
production optimization and quality improvement in the electronics industry
256. Alarousu, Erkki (2006) Low coherence interferometry and optical coherence
tomography in paper measurements
257. Leppäkoski, Kimmo (2006) Utilisation of non-linear modelling methods in flue-
gas oxygen-content control
259. Sorvoja, Hannu (2006) Noninvasive blood pressure pulse detection and blood
pressure determination
Book orders: Distributed by
OULU UNIVERSITY PRESS OULU UNIVERSITY LIBRARY
P.O. Box 8200, FI-90014 P.O. Box 7500, FI-90014
University of Oulu, Finland University of Oulu, Finland
C261etukansi.fm Page 1 Tuesday, November 21, 2006 10:18 AM

OULU 2006

C 261
C 261

ACTA
UNIVERSITY OF OULU P.O. Box 7500 FI-90014 UNIVERSITY OF OULU FINLAND

ACTA
U N I V E R S I T AT I S O U L U E N S I S

C
A C TA U N I V E R S I TAT I S O U L U E N S I S

S E R I E S E D I T O R S
Mika Huuhtanen TECHNICA

ASCIENTIAE RERUM NATURALIUM

ZEOLITE CATALYSTS IN

Mika Huuhtanen
Professor Mikko Siponen

BHUMANIORA THE REDUCTION OF NOX IN

LEAN AUTOMOTIVE EXHAUST
Professor Harri Mantila

CTECHNICA
Professor Juha Kostamovaara GAS CONDITIONS
DMEDICA
Professor Olli Vuolteenaho BEHAVIOUR OF CATALYSTS IN ACTIVITY,
DRIFT AND TPD STUDIES
ESCIENTIAE RERUM SOCIALIUM
Senior Assistant Timo Latomaa

FSCRIPTA ACADEMICA
Communications Officer Elna Stjerna

GOECONOMICA
Senior Lecturer Seppo Eriksson

EDITOR IN CHIEF
Professor Olli Vuolteenaho
EDITORIAL SECRETARY
Publications Editor Kirsti Nurkkala FACULTY OF TECHNOLOGY,
DEPARTMENT OF PROCESS AND ENVIRONMENTAL ENGINEERING,
UNIVERSITY OF OULU
ISBN 951-42-8285-X (Paperback)
ISBN 951-42-8286-8 (PDF)
ISSN 0355-3213 (Print)
ISSN 1796-2226 (Online)