Applied Catalysis B: Environmental 36 (2002) 261–277

Combinatorial preparation and high-throughput catalytic tests

of multi-component deNOx catalysts
M. Richter∗ , M. Langpape, S. Kolf, G. Grubert, R. Eckelt,
J. Radnik, M. Schneider, M.-M. Pohl, R. Fricke
Institut für Angewandte Chemie, Berlin-Adlershof e.V., Richard-Willstätter-Str. 12, D-12489 Berlin, Germany
Received 24 March 2001; received in revised form 13 May 2001; accepted 30 September 2001
Dedicated to Prof. Dr. B. Lücke on the occasion of his 65 birthday.

Abstract
A quaternary catalyst library of 56 samples comprising all combinations of four elements, viz. Ag, Co, Cu, In, with six equally
spaced atomic fraction increments from 0 to 1 was prepared by impregnation of a proprietary mesoporous alumina support.
Catalytic properties of the library were tested in the selective catalytic reduction (SCR) of NOx by propane under lean conditions
in the temperature range 400–500 ◦ C. The catalytic data acquired by a parallel 64-channel microreactor system with automated
time-of-flight mass spectrometric analysis have been evaluated regarding selectivity–compositional relationships, synergistic
effects for NOx conversion, and efficiency of propane utilization. Full conversion of NOx is achieved over Ag–Co combinations
at 450 ◦ C with N2 selectivities of more than 90% and reductant utilization of 20% in a feed of 1500 ppm NO, 1500 ppm propane
and 5 vol.% O2 (space velocity of 36,000 cm3 gcat −1 h−1 ). For the single-component catalysts Ag/Al2 O3 , Co/Al2 O3 , Cu/Al2 O3 ,
and In/Al2 O3 , the state of the elements on the mesoporous alumina was characterized by X-ray diffraction (XRD), X-ray
photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). Cobalt forms a spinel-like cobalt aluminate
phase whereas copper and indium are present as oxides with small sizes not detectable by XRD. Silver occurs in both metallic
state and as Ag2 O, and forms Agn clusters of at least two different sizes, predominantly with diameters of about 30 nm. The
conclusions are consistent with the reducibility of the single-component catalysts samples by H2 . Surface area measurements
and pore size distributions revealed reasonable modifications of the textural properties. The main pore size of the alumina
support is decreased from 7 to ca. 5 nm after loading of the active components. © 2002 Elsevier Science B.V. All rights reserved.
Keywords: SCR of NOx by propane; Combinatorial heterogeneous catalysis; Noble metal-free catalysts; Catalyst library; Multi-channel
reactor system

1. Introduction worldwide [1–3]. These multi-functional catalyst

The development of deNOx automotive catalysts
which are active in excess of air (corresponding to
lean operating conditions of combustion engines at
λ > 1) is a primary target of current research work
∗ Corresponding author.
E-mail address: mr@aca-berlin.de (M. Richter).
formulations contain precious metals for the three-way
function (hydrocarbon, CO and NOx abatement) at
stoichiometric or fuel-rich conditions, supplemented
by alkali- or alkaline-earth components for NOx stor-
age under lean conditions [4–6]. During the NOx
storage lean cycle, NO is oxidized at the noble metal
component of the catalyst to form NO2 which then
reacts with the storage component forming nitrate.

0926-3373/02/$ – see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 3 3 7 3 ( 0 1 ) 0 0 2 9 0 - 9
262 M. Richter et al. / Applied Catalysis B: Environmental 36 (2002) 261–277
For regeneration, the engine is shortly operated at
a stoichiometric air/fuel ratio [7]. Concerning NOx
abatement from diesel engines one strategy is the ad-
dition of hydrocarbon reductants in the exhaust gas.
The main component of the catalyst aimed at low
temperature operation with hydrocarbon reductant
in passenger cars is platinum supported on alumina.
High temperature heavy duty applications need no-
ble metal-free catalysts preferentially. The concept of
selective catalytic reduction (SCR) of NOx requires
reasonable amounts of hydrocarbons in the exhaust
gas. Normally, the hydrocarbon concentration at the
engine outlet is low and not sufficient for effective
NOx conversion. As a consequence, hydrocarbons
have to be supplied by adding secondary fuel into
the exhaust pipe. Lab-scale investigations with model
exhaust gases most frequently use propane, propene
or mixtures of the two hydrocarbons. Elements from
the periodic table groups 8 (Co), 11 (Cu, Ag, Au), 13
(Ga, In) and 14 (Sn) supported on alumina have been
reported to be active for operation temperatures be-
tween 350 and 500 ◦ C under fuel-lean conditions for
NOx conversion with propane/propene and methane
[8–15]. Investigations focus on single-component cat-
alysts whereas nearly no attempts have been described
to involve multi-component catalyst formulations by
combining several of the active elements on the alu-
mina support. Not least one reason is that the number
of possible combinations if considering the loading
as additional variable is enormously high, even with
a limited number of active components. Progress in
high-throughput testing with parallel reactors and
short analysis times rendered possible the screening
of a large number of catalysts within short times
[16]. One application of combinatorial catalysis to the
selective reduction of NO has been reported by Krantz
et al. [17]. Starting with four components, a set of
catalysts has been prepared whose composition re-
sulted from a combination of the elements Pt, Rh, In
and Na supported on ␥-alumina. It turned out that NO
conversions by propene of 70% are achievable in a
narrow temperature range between 300 and 400 ◦ C for
compositions containing 6–8 wt.% Na, 0.4–0.6 wt.%
Pt, and 0.2–0.4 wt.% Pd. Active catalysts are pre-
dominantly indium-free. C3 H6 consumption and CO2
formation in parallel confirm that Pt is very active
for hydrocarbon oxidation at low temperatures (50%
conversion at 300 ◦ C, 100% conversion at 350 ◦ C)
even under fuel-rich conditions (1.575 vol.% O2 in the
feed) whereas Pd gains activity at higher temperatures.
Indium and sodium have no oxidation activity at all.
The approach we have chosen differs in several
points from that one reported. (i) The working temper-
ature of the catalysts aimed at was from 400 to 500 ◦ C.
This means that precious metal components are not
suitable as constituents of the catalyst. (ii) The cata-
lysts should operate under lean conditions, i.e. with
oxygen excess. (iii) A mesoporous aluminum oxide
should be taken as support. Due to the ordered struc-
ture and a higher surface area of this specific alumina
support, deposition of the active components should
lead to a highly dispersed coverage. The active ele-
ments chosen were Ag, Co, Cu and In as the most
prominent examples with deNOx activities at medium
and high reaction temperatures. A quaternary cata-
lyst library of 56 samples comprising all combinations
of the four elements with six equally spaced atomic
fraction increments from 0 to 1 was prepared by auto-
mated impregnation of a proprietary mesoporous alu-
mina support. Catalytic properties of the library were
tested in the selective catalytic reduction of NOx by
propane under lean conditions in the temperature range
400–500 ◦ C by a parallel 64-channel microreactor sys-
tem with automated time-of-flight mass spectrometric
analysis The analytic equipment allowed the balancing
of C- and N-containing components and enabled the
calculation of selectivity of the NOx conversion to N2 .
Single-component catalyst preparation were charac-
terized by N2 adsorption, X-ray diffraction (XRD),
transmission electron microscopy (TEM), temper-
ature-programmed H2 reduction, and X-ray photo-
electron spectroscopy (XPS).
2. Experimental
2.1. The alumina support
Preparation of alumina followed the sol–gel
method described in [18] by controlled hydrolysis
of aluminum tri-sec-butylate, C12 H27 AlO3 (Merck-
Schuchardt, Germany) in the presence of structure
directing agents in non-aqueous solution. The pre-
cipitated solid was dried and calcined at 600 ◦ C for
2 h in air. The fine powder was subsequently pressed,
crushed and a fraction between 200 and 500 ␮m has
 M. Richter et al. / Applied Catalysis B: Environmental 36 (2002) 261–277 263

been sieved out and used for catalyst preparation. Table 1

To simulate the influence of the impregnation pro- Catalyst samples of the 56 member library
cedure, a part of the support has been impregnated Catalyst no. Loading (atomic fractions)
with distilled water, dried and calcined again. The In Ag Co Cu
alumina support and the single-component catalysts
were characterized by N2 adsorption for their surface 01 0 0 1 0
02 0.2 0 0.8 0
areas, pore volumes and average pore diameters. 03 0 0.2 0.8 0
04 0.4 0 0.6 0
2.2. Preparation of the catalyst library 05 0.2 0.2 0.6 0
06 0 0.4 0.6 0
Ag, Co, Cu and In were chosen as active ele- 07 0.6 0 0.4 0
08 0.4 0.2 0.4 0
ments for reasons discussed in Section 1. Solutions 09 0.2 0.4 0.4 0
were prepared by solving AgNO3 , Co(NO3 )2 ·6H2 O, 10 0 0.6 0.4 0
Cu(NO3 )2 ·3H2 O and In(NO3 )3 ·6H2 O (all from 11 0.8 0 0.2 0
Aldrich, Germany) in distilled water to yield a 1 M 12 0.6 0.2 0.2 0
solution. The catalyst library comprises all possible 13 0.4 0.4 0.2 0
14 0.2 0.6 0.2 0
combinations of the four elements in six concentra- 15 0 0.8 0.2 0
tion increments taken as atomic fractions

xi in steps 16 1 0 0 0
of 0.2 from 0 to 1 with the limitation xi = 1. From 17 0.8 0.2 0 0
this approach, a library results comprising 56 samples 18 0.6 0.4 0 0
with different compositions. The maximum loading 19 0.4 0.6 0 0
was set to 0.5 mmol g−1 leading to single-component
20 0.2 0.8 0 0
21 0 1 0 0
catalyst samples of 5.00 wt.% Ag/Al2 O3 , 2.95 wt.% 22 0 0 0.8 0.2
Co/Al2 O3 , 3.20 wt.% Cu/Al2 O3 , and 5.52 wt.% 23 0.2 0 0.6 0.2
In/Al2 O3 . 24 0 0.2 0.6 0.2
The catalysts have been prepared by impregnation 25 0.4 0 0.4 0.2
26 0.2 0.2 0.4 0.2
of the mesoporous alumina support on the synthe- 27 0 0.4 0.4 0.2
sis robot SOPHAS (Zinsser Analytik, Germany) 28 0.6 0 0.2 0.2
with different quantities of the nitrate solutions. The 29 0.4 0.2 0.2 0.2
impregnation was performed as incipient wetness. 30 0.2 0.4 0.2 0.2
The capacity of the solid to absorb solution until com- 31 0 0.6 0.2 0.2
32 0.8 0 0 0.2
plete wetness was determined by preliminary mea- 33 0.6 0.2 0 0.2
surements and amounted to 1 cm3 g−1 . The volume of 34 0.4 0.4 0 0.2
solution was adjusted, if necessary, by dilution with 35 0.2 0.6 0 0.2
distilled water. After impregnation, the set of catalysts 36 0 0.8 0 0.2
was calcined in an oven at 550 ◦ C for 2 h. Catalyst 37 0 0 0.6 0.4
38 0.2 0 0.4 0.4
samples are listed in Table 1. The numbers given will 39 0 0.2 0.4 0.4
be used throughout the work for abbreviation. 40 0.4 0 0.2 0.4
41 0.2 0.2 0.2 0.4
2.3. Catalytic measurements 42 0 0.4 0.2 0.4
43 0.6 0 0 0.4
44 0.4 0.2 0 0.4
Catalytic experiments were carried out in a catalyst 45 0.2 0.4 0 0.4
testing system using a multi-channel reactor. The re- 46 0 0.6 0 0.4
actor is made of ceramic blocks containing 64 reaction 47 0 0 0.4 0.6
channels with a diameter of 5 mm in three concentric 48 0.2 0 0.2 0.6
circles. An inner and an outer heating ensured a good 49 0 0.2 0.2 0.6
50 0.4 0 0 0.6
isothermal zone in the whole ceramic block. The 51 0.2 0.2 0 0.6
reaction channels are comparable to classical fixed
264 M. Richter et al. / Applied Catalysis B: Environmental 36 (2002) 261–277
Table 1 (Continued )
Catalyst no. Loading (atomic fractions)
In Ag Co Cu
52 0 0.4 0 0.6
53 0 0 0.2 0.8
54 0.2 0 0 0.8
55 0 0.2 0 0.8
56 0 0 0 1
bed reactors. They were operated at or slightly above
ambient pressure. Catalyst samples (mcat = 0.1 g,
d p = 200–500 ␮m) are placed on stainless steel
grids. A similar flow through the parallel reactors is
achieved by a quartz powder bed in each channel giv-
ing the same pressure drop across the reactor block.
All channels are permanently on stream, and they are
connected to the analytical instrument by a system of
multi-port valves that allows a sequential analysis of
the exit stream of each reaction channel. The on-line
analyses of the product stream are accomplished on
a combination of a fast gas chromatography (GC)
and a time-of-flight mass spectrometer (TOF-MS).
The GC provides a partial separation of the differ-
ent products which might be easily analyzed by the
TOF-MS. This combination enables the analysis of
NO, N2 , N2 O, propane, propene, CO, CO2 five times
in less than 3 min. A complete analysis of the entire
library of 64 catalysts required about 2.5 h. Fur-
ther technical details are described elsewhere [19].
Reaction temperatures have been varied between 400
and 500 ◦ C. The reaction mixture consisting of NO
(1500 ppm), C3 H8 (1500 ppm), O2 (5%) and helium
(balance) passed the catalysts at a total flow rate of
60 ml (STP) min−1 corresponding to a gaseous hourly
space velocity (GHSV) of 36,000 cm3 gcat −1 h−1 .
2.4. Data representation
The NO conversion (in %) is given by XNO
= 100(cNO,in − cNO,out )/cNO,in where cNO,in and
cNO,out are the concentrations of NO at the reactor
inlet and outlet, respectively. Correspondingly, the
overall propane conversion is formulated. On the basis
of product concentrations a balance of N-containing
components and C-containing products has been cal-
culated leading to values of 100% with good accuracy
(±5%). The selectivity of the reaction can be ex-
pressed by different terms. N2 selectivity is understood
as the percentage of NO converted to N2 , expressed
as (SN = 100(cN2 /XNO ). Formation of undesired ni-
trous oxide is the main side reaction to be considered.
The extent of CO and propene formation is accounted
for by the percentage S CO = 100(cCO /Xpropane ) and
S propene = 100(cpropene /Xpropane ), respectively.
Synergistic effects will be judged to exist if experi-
mentally observed NOx conversions for multi-compo-
nent catalyst formulations deviate from hypothetical
values calculated from results of the single-component
catalysts assuming additive contributions to the over-
all activity. Taking the experimentally determined
NO conversions of the single-component catalyst
samples, a NOx conversion X is calculated for
all multi-component catalyst samples according to
Eq. (1)
X = xAg XAg + xCo XCo + xCu XCu + xIn XIn (1)
where xi is the atomic fraction of the given element
and Xi the conversion achieved by the given single-
component catalyst.
The utilization of propane for reduction of NO is of
interest, besides the competing oxidation to CO and
CO2 in excess oxygen, because fuel saving is higher
with lower percentages of reductant oxidation. Oxi-
dation of propane by oxygen is given by the reaction
stoichiometry
C3 H8 + 0.5(3z + 4)O2 → 3COz + 4H2 O (2)
considering CO and CO2 as oxidation products with
z = (nCO + 2nCO2 )/(nCO + nCO2 ). Formally, the
SCR of NO by propane is equivalent to oxidation of
propane by nitrogen monoxide (Eq. (3)).
C3 H8 + (3z + 4) NO
→ 0.5(3z + 4)N2 + 3COz + 4H2 O (3)
This stoichiometry represents a borderline value
where the reaction between propane and nitrogen
monoxide is accomplished without participation of
gas phase oxygen. If z = 2, 1 mol of propane should
convert 10 mol of NO. However, preliminary exper-
iments showed that NO reduction without gas phase
oxygen does not proceed on the single-component
catalysts. Hence, at least 0.5 mol O2 is necessary
to enable initial oxidation of NO to NO2 (Eq. (4)).
 M. Richter et al. / Applied Catalysis B: Environmental 36 (2002) 261–277
NO2 as strong oxidizing agent converts propane, and
becomes simultaneously reduced to N2 (Eq. (5)).
NO + 0.5O2 ↔ NO2
C3 H8 + 0.5(3z + 4)NO2
→ 0.25(3z + 4)N2 + 3COz + 4H2 O
Linking both reaction steps after adjusting the
stoichiometric factors, Eq. (6) describes the overall
process where 1 mol of propane is able to convert
between 3.5 mol NO (z = 1) and 5 mol NO (z = 2).
C3 H8 + 0.5(3z + 4)NO + 0.25(3z + 4)O2
→ 0.25(3z + 4)N2 + 3COz + 4H2 O
2.5. Accompanying catalyst characterization
2.5.1. Surface areas and pore volumes
Surface areas and pore volumes of the support and
the single-component catalyst samples were deter-
mined by nitrogen adsorption on the ASAP 2010M
facility (Micromeritics). The samples were kept at
400 ◦ C under vacuum (0.13 Pa) for 4 h before starting
N2 adsorption at liquid nitrogen temperature. Calcu-
lation of pore sizes followed the method of Barrett–
Joyner–Halenda (BJH) [20] according to implemented
software routines using the Halsey thickness equation
[21] for relating the thickness of the adsorbed layer
to the relative pressure. All calculations are based on
the desorption model.
2.5.2. X-ray diffraction measurements
XRD powder diffraction measurements were car-
ried out with a STOE powder diffraction system using
Cu K␣ radiation at room temperature.
2.5.3. Transmission electron microscopy
Electron microscopic images of samples were taken
by TEM applying the Philips CM20 microscope at
200 kV (LaB6 ). Specimens were prepared by trans-
ferring small quantities of the samples to microgrids
coated by Lacey carbon films. EDX analysis was
performed using a PV 9900 spectrometer (EDAX).
2.5.4. Temperature-programmed reduction (TPR)
Temperature-programmed reduction was perfor-
med applying the characterization system AMI-100
265
(Altamira Instruments) equipped with a thermal con-
ductivity detector. For reduction, a feed of 5% H2
in Ar was used at a heating rate of 5 K min−1 . The
(4)
overall flow rate amounted to 25 cm3 min−1 . The con-
sumption of H2 was determined from the integrated
peak areas by calibration.
(5)
2.5.5. X-ray photoelectron spectroscopy
XPS spectra of the single-component catalysts were
obtained using an ESCALAB 220iXL spectrometer
(VG Instruments) equipped with a monochromatic Al
K␣ X-ray source (1486.6 eV). The spectra were cor-
rected with respect to the Al 2p signal of the Al2 O3
support at 74.4 eV. For determination of the binding
(6) energies and the peak intensity a curve fitting has
been performed by combination of Lorentz and Gauss
curves after a Shirley background subtraction. Peak
intensities were normalized utilizing the sensitivity
factors of Scofield [22] and the transmission function
of the instrument. The XPS intensity ratios IMe /IAl
were calculated from the Co 2p, In 3d, Ag 3d and the
Cu 2p normalized peak areas, related to the Al 2p nor-
malized peak intensity. A surface concentration nMe
(mol%) is calculated as nMe = 100(IMe /(I Me + I Al )).
3. Results and discussion
3.1. Textural characterization
Textural information on the alumina support and the
single-component catalyst samples are summarized in
Table 2. Nitrogen adsorption isotherms are presented
in Fig. 1(a) indicating a moderate loss of surface area
caused by the preparation procedure. Largely, this
loss is already observed for the alumina after impreg-
nation with distilled water and analogous treatment
as applied for catalyst preparation. That means, the
observed textural modifications are only partly at-
tributable to a deposition of the active components.
This is reasonable considering the relatively low metal
loading. On the other side, a considerable loss of pore
volume is observed, accompanied by lower average
pore diameters. The pore size distribution shown in
Fig. 1(b) underlines the fact that the hydration and
calcination caused the major effect of the pore size
shift to smaller values, whereas the impregnation with
the active components lead to only minor changes.
266 M. Richter et al. / Applied Catalysis B: Environmental 36 (2002) 261–277

Table 2
Surface characterization of the mesoporous alumina support and the single-component catalysts Ag/Al2 O3 , Co/Al2 O3 , Cu/Al2 O3 , and
In/Al2 O3
Catalyst Surface area (m2 g−1 ) Pore volume (cm3 g−1 ) Pore diameter (nm)

Al2 O3 (compacted) 291 0.78 8.6

Al2 O3 (impregnated-dried) 265 0.58 6.7
5.00 wt.% Ag/Al2 O3 239 0.45 5.9
2.95 wt.% Co/Al2 O3 224 0.38 5.2
3.20 wt.% Cu/Al2 O3 255 0.41 4.8
5.52 wt.% In/Al2 O3 241 0.41 5.2

The XRD pattern (Fig. 2) show no diffraction lines
attributable to crystalline bulk oxide phases of the
supported metals nor to metallic silver in the case
of Ag/Al2 O3 . The amorphous character of the meso-
porous alumina support before calcination was con-
firmed (not shown). But, after catalyst preparation,
broad diffraction lines of low intensity at 2Θ = 45.9
and 37.6 indicate the presence of crystalline ␥-alumina.
This points to some detrimental influence of the prepa-
ration procedure on the amorphous alumina phase
structure. It has to be noted that the diffraction line at
2Θ = 37.6 is more intense in the case of Co/Al2 O3
than for other samples. Because spinel-like cobalt alu-
minate CoAl2 O4 has its most intense diffraction line
at 2Θ = 36.8 [23], a contribution from Co aluminate
might be responsible for the intensity enhancement.
3.2. Morphology
TEM images of the single-component catalysts
revealed nano-sized clusters in the case of Ag/Al2 O3
(Fig. 3) with predominant sizes of about 30 nm,
besides a few larger aggregates of 90–100 nm. Accor-
ding to EDX analysis, the clusters consist of metallic

Fig. 1. (a) Nitrogen adsorption isotherms of the alumina support after calcination at 600 ◦ C: (䊏) as prepared, (䊉) after impregnation with
distilled water, drying and calcining, and of the single-component catalysts (×) Ag/Al2 O3 (5.00 wt.%), (+) Co/Al2 O3 (2.95 wt.%), (䉬)
Cu/Al2 O3 (3.20 wt.%), and (䊊) In/Al2 O3 (5.52 wt.%). (b) Pore size distribution.
 M. Richter et al. / Applied Catalysis B: Environmental 36 (2002) 261–277 267

Fig. 2. XRD diagrams of single-component catalysts (a) Co/Al2 O3 , (b) In/Al2 O3 , (c) Ag/Al2 O3 , and (d) Cu/Al2 O3 .

silver. On the other side, temperature-programmed
reduction by H2 (see later) proved the existence of
reducible silver species, either Ag2 O or Ag+ , repre-
senting nearly 50% of the overall loading. Therefore,
silver should exist in highly dispersed Ag2 O and Ag+ ,
besides nano-sized silver clusters. Consequently, the
dispersion of silver after preparation is not uniform.
Clusters are also detectable by TEM for sample
In/Al2 O3 but, formation of indium oxide aggregates
takes place during measurement. This implies a

Fig. 3. TEM micrograph of single-component catalyst Ag/Al2 O3 .

268 M. Richter et al. / Applied Catalysis B: Environmental 36 (2002) 261–277

Cu/Al2 O3 . The reduction profile of Ag/Al2 O3 (no.

Fig. 4. H2 consumption profiles of TPR measurements of
single-component catalysts Ag/Al2 O3 (no. 21), Cu/Al2 O3 (no. 56),
Co/Al2 O3 (no. 01) and In/Al2 O3 (no. 16). Conditions: 5 vol.%
H2 /Ar, flow rate 25 cm3 min−1 , heating rate 5 K min−1 , catalyst
mass 0.1 g. Isothermal hold for 10 min at 800 ◦ C.
mobility with subsequent aggregation caused by the
electron beam. The time to accomplish the electron
image is sufficient to change the surface state of the
indium oxide. For this reason, the TEM picture is
not representative for the state of the indium after
preparation and during catalysis. The TEM pictures of
Co/Al2 O3 and Cu/Al2 O3 gave no indication of clus-
ters or surface metal oxide phases.
3.3. TPR measurements
Reduction profiles of the single-component cata-
lysts are presented in Fig. 4. After integration, the
overall consumption of hydrogen was calculated
and compared with amounts required for reasonable
changes of the valence state of the active components
as summarized in Table 3.
Qualitatively, it can be seen that the reduction is
not completed at 800 ◦ C, with exception of that for
21) reveals three overlapping peaks centered at about
100–120, 275 and 650 ◦ C. The peak at relatively low
temperatures is attributable to the reduction of Ag2 O.
H2 consumption during TPR in the temperature range
of 500–700 ◦ C is indicative for reduction of stabi-
lized Ag+ ions to Ag0 , at least in the case of zeolite
supports [24,25].
Reduction of Co/Al2 O3 (sample no. 01) proceeds
in a non-specific way with faint peaks of H2 con-
sumption at about 575 and above 800 ◦ C. The formal
reduction degree amounts to only 10% (cf. Table 3).
It is known [26] that cobalt ion diffusion into the
structure of alumina leads to species that are difficult
to reduce. This would imply a prevalent incorporation
of the impregnated Co into the support matrix with
high dispersion of Co ions. This supports the conclu-
sions drawn from XRD and XPS measurements that
a cobalt aluminate phase is formed after calcination.
Reduction of Cu/Al2 O3 (no. 56) is characterized
by one broad H2 consumption centered at 350 ◦ C.
Formation of CuO (black) is not dominant because
the color of the Cu/Al2 O3 remained blue-greenish
after calcination. Nevertheless, the consumption of
H2 corresponds to a complete accessibility of the Cu
for reduction from Cu2+ to Cu0 .
The reduction of In/Al2 O3 (no. 16) starts at about
175 ◦ C and is characterized by three overlapping
steps. Reduction is not completed even at 800 ◦ C.
This is significantly different from reduction profiles
reported for indium impregnated on pyrogenic silica
and for indium oxo cations ([InO]+ ) fixed to cationic
positions of zeolites [27]. The overlapping processes
cannot unambiguously be assigned to single reduc-
tion steps. Formally, the hydrogen balance allows a
complete reduction of In2 O3 to In2 O where the com-
plex shape of the reduction profile indicates a certain
heterogeneity of the impregnated indium species.

Table 3
Results of the TPR characterization for single-component catalyst formulations
Catalyst no. Catalyst Loading H2 consumed Reduction Valence change
(wt.%)a (mmol g−1 ) degree (%) assumed
21 Ag/Al2 O3 5.00 0.13 52 Ag+ → Ag0
01 Co/Al2 O3 2.95 0.05 10 Co2+ → Co0
56 Cu/Al2 O3 3.20 0.45 108 Cu2+ → Cu0
16 In/Al2 O3 5.52 0.56 112 In3+ → In+
a Corresponding to 0.50 mmol g−1 .
 M. Richter et al. / Applied Catalysis B: Environmental 36 (2002) 261–277 269

Fig. 5. XPS spectra of single-component catalysts Ag/Al2 O3 , Co/Al2 O3 , Cu/Al2 O3 and In/Al2 O3 ; sat. denotes satellites.

Considering the TEM results, a modification of the In
state during the TPR run cannot be excluded.
3.4. XPS characterization
XPS spectra of the single-component catalysts are
presented in Fig. 5. Binding energies (BE), IMe /IAl
surface ratios, surface concentrations and assignments
are listed in Table 4.
The Ag 3d5/2 binding energy of sample Ag/Al2 O3
at 368.0 eV has to be compared with binding ener-
gies of 368.3 and 367.5 eV for metallic silver and
Ag2 O, respectively [10,24,28]. Thermally, bulk Ag2 O
decomposes to Ag metal at higher temperatures
[28]. A comparison of binding energies of sample
Ag/Al2 O3 with the literature data favors metallic sil-
ver although the peak width published for metallic
silver and silver oxide peaks are around 1 eV whereas

Table 4
Results of the XPS characterization for single-component catalyst formulations
Catalyst No. Peak BE (eV) IMe /IAl a nMe /n(Me+Al) (mol%) Valence state Compound

Ag/Al2 O3 21 Ag 3d5/2 368.0 0.0496 0.047 Ag0 /Ag+ Ag, Ag2 O

Co/Al2 O3 01 Co 2p3/2 780.8 0.0820 0.076 Co2+ CoAl2 O4
Cu/Al2 O3 56 Cu 2p3/2 933.9 0.0887 0.081 Cu2+ CuO
In/Al2 O3 16 In 3d5/2 445.3 0.2767 0.217 In3+ In2 O3
a The theoretical value at homogeneous metal distribution throughout the alumina bulk phase amounts to 0.025.
270 M. Richter et al. / Applied Catalysis B: Environmental 36 (2002) 261–277
the experimental value for Ag/Al2 O3 amounts to
2.4 eV. The Ag surface concentration resulting from
XPS analysis is near to the homogeneous bulk distri-
bution what is unlikely because of the impregnation
method applied for preparation. Moreover, location
of silver at the alumina surface is documented by
TEM results. Because the size of the Ag clusters is
larger than the penetration depth of the photo elec-
trons (30 nm versus 2 nm), it is concluded that not all
of the silver inside the clusters is detected by XPS.
This leads to the low IAg /IAl surface ratio.
Sample Co/Al2 O3 revealed a Co 2p3/2 binding
energy of 780.8 eV that is higher than characteristic
for Co3 O4 (780.0 eV) and CoO (780.1 eV) [28,29]. A
binding energy of 781.9 eV is reported for cobalt alu-
minate [12,29]. Ji et al. [30] attributed the Co 2p peak
at 782.0 eV of 10 wt.% Co impregnated on sol–gel
derived alumina to a CoAl2 O4 phase. Although ther-
mal decomposition of Co nitrate preferably leads to
Co3 O4 , the interaction of Co species with the alu-
mina surface results in formation of bulk Co alumi-
nate by Co2+ diffusion into the alumina framework
depending on the alumina reactivity and temperature
of calcination [30].
The observed shift of binding energies to higher
values indicates the presence of surface Co2+ , proba-
bly located by a cobalt aluminate-like phase. This is
reconcilable with the poor reducibility stated by TPR,
because reduction of Co2+ in CoAl2 O4 is more diffi-
cult than that of Co3 O4 due to the stronger interaction
with the support.
The Cu 2p3/2 peak at 933.9 eV found for sample
Cu/A2 O3 corresponds to that one reported for bulk
CuO (934.1 eV) [29]. Additionally, satellite struc-
tures typical for CuO were observed. The existence
of Cu+ ions as well as metallic Cu can be excluded.
Moreover, there are no indications supporting the ex-
istence of CuAl2 O4 which has XPS Cu 2p3/2 binding
energies of 935 eV [23,31]. It is concluded that the
surface phase of sample Cu/Al2 O3 is equivalent to
CuO. The CuO phase is X-ray amorphous, and should
be finely dispersed because TEM could not prove the
existence of aggregates at the surface of the support.
Nevertheless, enrichment of Cu at the alumina surface
follows from the ICu /IAl surface ratio, comparable to
the value observed for Co/Al2 O3 .
A binding energy of 445.3 eV was measured for
In 3d5/2 of sample In/Al2 O3 . This value is close to
that reported for indium in In2 O3 (444.4 eV) [29].
Indium at the catalyst surface should be located in
an In2 O3 bulk phase environment, although no crys-
talline In2 O3 could be detected by XRD. The In sur-
face concentration is the highest, compared with the
other single-component catalysts and implies that no
indium has penetrated into subsurface regions. TEM
investigations prove that aggregates are formed during
acquisition of the micrograph. However, the initial
dispersion of In2 O3 after sample preparation should
be higher and aggregation under the oxidizing cat-
alytic conditions at normal pressure is unlikely. The
H2 -TPR profile showed full accessibility of indium
and nearly quantitative reduction from In3+ to In+ .
3.5. Catalytic results
3.5.1. Activities and selectivities
The properties of the single-component composi-
tions are summarized in Fig. 6(a–d). Ag/Al2 O3 has the
highest activity achieving full conversion at ca. 475 ◦ C,
whereas In/Al2 O3 is the single-component catalyst
with the lowest activity. The selectivity SN amounts to
90% at minimum, i.e. the reaction proceeds selectively
to N2 without noticeable N2 O formation. Also, a de-
sirable low selectivity of CO formation is maintained
by the single-component catalyst formulations with
exception of In/Al2 O3 where SCO reaches a maximum
of 40% at low temperature. Although, at higher re-
action temperatures, SCO decreases to approximately
10% at 475 ◦ C. Interestingly, Co/Al2 O3 shows a high
percentage of propene formation at low temperatures
obviously resulting from oxidative dehydrogenation
of propane. Correspondingly, CO2 formation is the
least observed for the single-component samples.
The NOx conversion levels for all catalyst compo-
sitions are presented in Fig. 7(a–d). The corners of the
pyramid represent the single-component catalysts and
the gradation is done in steps of 0.2 representing the
six concentration steps in atomic fractions from 0 to 1.
For all members of the catalyst library, no NO2
was detected in the exit stream. This might have sev-
eral reasons. (i) The NO/NO2 equilibrium (Eq. (4)) is
shifted to NO2 dissociation with increasing tempera-
tures. At maximum, 20% NO2 are present in a NO
(950 ppm)/O2 (2%) mixture at 450 ◦ C. This percentage
decreases to approximately 10% at 500 ◦ C [13]. (ii)
Due to its intermediary character, NO2 , once formed,
 M. Richter et al. / Applied Catalysis B: Environmental 36 (2002) 261–277 271

Fig. 6. Catalytic results for single-component catalysts (a) Ag/Al2 O3 , (b) Co/Al2 O3 , (c) Cu/Al2 O3 , and (d) In/Al2 O3 in the 64-channel
reactor. NOx conversion, (䊉); propane conversion, (䊊); N2 selectivity, (䉱); propene selectivity, (×); CO selectivity, (䉬); N2 O selectivity,
(䉲). Feed 1500 ppm NO, 1500 ppm propane, 5 vol.% O2 , GHSV = 36,000 cm3 gcat −1 h−1 .

is further converted to N2 . (iii) To a certain extent, the
lack of NO2 will be associated with the specific of
GC–MS analysis if NO2 is transformed into N2 and
O2 inside the mass spectrometer.
It follows from Fig. 7(a–d) that active catalyst for-
mulations are rich in Ag and poor in Cu. Samples
containing a high percentage of In are generally less
active than others. The pure alumina support, calcined
at 600 ◦ C, yields 8–10% NOx conversion at 500 ◦ C.
At lower temperatures, contribution of the support to
the deNOx activity of the catalysts is negligible.
Selectivity values SN are near 100% for almost
all catalyst samples and decrease to a minimum of
90% over Ag-rich catalysts at higher reaction tem-
peratures. Correspondingly, N2 O formation is always
lower than 10%. As already follows from the catalytic
test results of single-component catalyst samples, the
SCR of NOx by propane over In/Al2 O3 is charac-
terized by a high percentage of CO formation. Thus,
also In-containing multi-component catalyst samples
reveal the highest CO selectivity. One example is
given in Table 5 for a reaction temperature of 425 ◦ C.
These 10 catalysts with the highest CO selectivities
contain In but no or less Cu. If Cu is present in higher
concentrations, CO will be oxidized to CO2 . On the
other side, propene is observed on catalysts having a
high percentage of Co but no Cu (cf. Table 6).
It turned out that the optimum catalyst is composed
by Co and Ag in approximately equal concentrations,
because at 425 ◦ C catalyst no. 06 (0.4 Ag, 0.6 Co) and
no. 10 (0.6 Ag, 0.4 Co) reveal the highest activities, ca.
70% NOx conversion, besides the single-component
catalyst samples Ag/Al2 O3 and Co/Al2 O3 .
The relatively high concentration of propene
observed for the Co/Al2 O3 single-component cata-
lyst is attributed to the low oxidation activity of the
CoAl2 O4 phase despite the large oxygen excess app-
lied. Therefore, propene is provided as an alternative
272 M. Richter et al. / Applied Catalysis B: Environmental 36 (2002) 261–277

Fig. 7. NOx conversion (gray-scale) of the 56-membered catalyst library at (a) 400 ◦ C, (b) 425 ◦ C, (c) 450 ◦ C, and (d) 475 ◦ C. Feed
1500 ppm NO, 1500 ppm propane, 5 vol.% O2 , GHSV = 36,000 cm3 gcat −1 h−1 . Catalyst enumeration according to Table 1.
 M. Richter et al. / Applied Catalysis B: Environmental 36 (2002) 261–277 273

Table 5 tion (1000 ppm NO, 1000 ppm propene, 5 vol.% O2 )

Multi-component catalyst samples with highest CO selectivities at are fairly comparable to the conditions applied in the
425 ◦ C
present work, with exception of the higher space veloc-
Catalyst no. Composition (atomic fractions) SCO ity and the different reductant (propene). NOx conver-
Ag Co Cu In
(%)
sion levels of more than 90% at 450 ◦ C had been found
16 0 0 0 1.0 44.5
if the catalyst was calcined at appropriate high tem-
17 0.2 0 0 0.8 43.4 peratures (600 or 700 ◦ C). In comparison to the mea-
11 0 0.2 0 0.8 40.1 surements presented in this work, the NOx conversion
07 0 0.4 0 0.6 38.2 versus temperature profile seems to be shifted by 50 ◦ C
12 0.2 0.2 0 0.6 30.1 to lower temperatures. But this is attributable to the
33 0.2 0 0.2 0.6 29.1
08 0.2 0.4 0 0.4 28.2
propene reductant, because olefins are more reactive
30 0.4 0.2 0.2 0.2 26.5 than alkanes in SCR chemistry. The Ag-impregnated
35 0.6 0 0.2 0.2 26.4 Al2 O3 was found considerably less active.
04 0 0.6 0 0.4 25.7 A thorough study on Co/Al2 O3 deNOx catalysts
was published in Ref. [13] involving Al2 O3 sup-
ports of different provenience and varied Co contents
reductant, besides the propane fed. Involvement of from 2 to 5 wt.%. Catalytic results reported by Yan
Cu affects adversely the reaction because propane is et al. [13] for lean NOx reduction with propane over
preferentially oxidized to CO2 . Indium leads to inter- Co/Al2 O3 are in fair agreement with results reported
mediate formation of CO which may serve as further in this work, despite diverging space velocity (12,000
reductant for NOx . versus 36,000 cm3 gcat −1 h−1 ) and feed composition
Reference data for single-component catalysts are (1.7% H2 O versus no H2 O added). Yan et al. [13]
available, but direct comparison is difficult due to used a ␥-Al2 O3 prepared by a sol–gel method which,
varying reaction conditions and reductants. Seker et al. however, is different to the preparation route of alu-
[10] studied the SCR of NOx by propene on a 5 wt.% mina applied in the present investigation. The authors,
Ag/alumina catalyst prepared by various methods, by physicochemical characterization, got evidence for
e.g. co-precipitation, a one step sol–gel process, and the existence of four different Co species at 5 wt.%
impregnation of alumina by silver nitrate. The authors loading, Co2+ in CoAl2 O4 , small Co3 O4 particles
reported the highest activity for the sample prepared strong interacting with the support, large Co3 O4 par-
by a sol–gel process. This process is not comparable ticles, and dispersed surface Co2+ ions in octahedral
with the synthesis procedure of the alumina support coordination. The latter Co2+ species are proposed to
described in this work because Seker et al. [10] per- be the most active species. From TPR measurements
formed the hydrolysis of the aluminum alkoxides in with H2 , the authors concluded that tetrahedrally co-
the presence of silver nitrate in aqueous solution. ordinated Co2+ ions in CoAl2 O4 are not reducible
Nevertheless, Ag loading (5 wt.%) and feed composi- below 800 ◦ C. This is in line with TPR results of
Co/Al2 O3 shown in Fig. 4.
Results reported by Maunula et al. [15] included In,
Table 6 Ag and Co catalysts prepared on sol–gel alumina that
Multi-component catalyst samples with highest propene selectivi- consisted mainly of ␥-Al2 O3 after final calcination
ties at 425 ◦ C
at 600 ◦ C. The 3.3 wt.% In/Al2 O3 sample achieved
Catalyst no. Composition (atomic fractions) Spropene nearly 100% NOx conversion to N2 at 400 ◦ C with
(%)
Ag Co Cu In dry feed (1000 ppm NO, 1000 ppm propene, 10 vol.%
02 0 0.8 0 0.2 33.1 O2 ) at a space velocity of 20,000 cm3 gcat −1 h−1 . The
28 0 1.0 0 0 31.3 Co/Al2 O3 sample (1.75 wt.%) revealed intermedi-
03 0.2 0.8 0 0 27.7 ate activity (ca. 60% at 400 ◦ C) whereas Ag/Al2 O3
06 0.4 0.6 0 0 16.2 (3.14 wt.% Ag) had only 10% conversion of NOx to
20 0.8 0 0 0.2 2.3
N2 but the highest oxidation activity for propene. A
10 0.6 0.4 0 0 0.1
pre-calcination of the Ag/Al2 O3 sample at 800 ◦ C
274 M. Richter et al. / Applied Catalysis B: Environmental 36 (2002) 261–277

improved the activity considerably. The authors sug-
gested that finely dispersed silver oxide particles still
existed on the sol–gel alumina calcined at 600 ◦ C
but larger silver and silver aluminate particles were
formed during high-temperature calcination sup-
pressing the total hydrocarbon oxidation, thus, en-
hancing the NOx conversion. We got no evidence
for the existence of a silver aluminate phase in the
single-component Ag/Al2 O3 catalyst. Nevertheless,
Ag/Al2 O3 was found highly active for the SCR of
NOx . The good performance may be attributed to the
predominance of nano-sized silver clusters.
3.5.2. Synergistic effects
To evaluate synergistic effects in NOx conversions,
the data base was screened for the differences between
experimentally observed NOx conversions and those
calculated by Eq. (1). Results are shown for the 56
catalysts in Fig. 8(a–d).
It is obvious that the majority of the multi-compo-
nent catalyst samples is less active than expected from
the sum of single-component contributions because
the difference (XNO,exp − XNO,cal ) is negative by
60–70 points. On the other side, there are catalyst
samples where experimental NOx conversions are
higher than expected from the sum of contributions
according to Eq. (1). It is striking that this effect is
mostly observed for sample numbers up to 20, that is
for Cu-free catalysts. Starting with catalyst number 22
that contains 0.2 atomic fraction of Cu, a tremendous
deterioration of the experimental NOx conversions are
recognizable, although with some exceptions which,
however, do not exceed 10–15 points at the highest
reaction temperature of 475 ◦ C. Further compositional
Cu-free variants tend to show good NOx conversion if
they mainly contain Ag and Co. A synergistic effect if
being associated with kinetic phenomena should rea-
sonably depend on the reaction temperature. This is

Fig. 8. Differences of experimental NOx conversions and pre-calculated conversions on the basis of results from single-component catalysts
Ag/Al2 O3 , Co/Al2 O3 , Cu/Al2 O3 and In/Al2 O3 at (a) 475 ◦ C, (b) 450 ◦ C, (c) 425 ◦ C, and (d) 400 ◦ C.
 M. Richter et al. / Applied Catalysis B: Environmental 36 (2002) 261–277 275

Table 7
NOx conversions of samples 20 and 21
Catalyst no. Composition (atomic factions) NOx conversion (%) at different temperatures (◦ C)

In Ag 400 425 450 475

20 0.2 0.8 28.4 72.0 100.0 98.8

21 0 1.0 27.1 66.0 95.5 92.8

the case, e.g. for sample 20 where deviations are +4.6, combinations of Co, Ag and In operate above the av-
+18.1, +21.3 and +20.6 at 400, 425, 450 and 475 ◦ C, erage 1:1 stoichiometry. Cu-containing catalysts keep
respectively. a 1:1 ratio at 425 ◦ C, cf. e.g. the single-component
Catalyst 20 is composed of 0.8 atomic fraction of catalyst, no. 56. But at higher reaction temperatures
Ag and 0.2 of In and its catalytic performance is almost (475 ◦ C, Fig. 9(b)), the Cu single-component catalyst
completely that of the pure silver single-component
catalyst formulation, catalyst no. 21 (Table 7).
Because the overall loading is fixed to a constant
value, the dependence of the reaction on the Ag load-
ing in the Ag/Al2 O3 formulation is not investigated.
Therefore, it cannot be decided whether the presence
of indium is necessary to keep the NOx conversion of
the 0.8 Ag/Al2 O3 catalyst near to the 1.0 Ag/Al2 O3
single-component catalyst.

3.5.3. NOx versus propane conversion

NOx versus propane conversion for the catalyst
library studied in this work are displayed in Fig. 9(a
and b) for 425 and 475 ◦ C, respectively. The dotted
lines indicate the 1:1 ratio between the conversions.
According to the assumed stoichiometry that 1 mol
of propane is able to reduce up to 5 mol of NOx , the
dotted lines means 20% utilization of propane for the
SCR of NOx and 80% of competing propane oxida-
tion. It has to be noted that an estimation of reductant
utilization often refers to the stoichiometry
2NO + 4O2 + C3 H8 → N2 + 3CO2 + 4H2 O (7)
leading to a value of 50% reductant utilization if NOx
and reductant conversions are equal. Without knowl-
edge how much oxygen in carbon oxides and water
originates from NO, various stoichiometries are plau-
sible. On the basis of the approach given, the pattern
of Fig. 9 implies an average utilization of the reductant
of about 20% with some exceptions in dependence on
Fig. 9. NOx vs. propane conversion for (a) 425 ◦ C, and (b) 475 ◦ C.
the reaction temperature. At the lower reaction temper-
Feed composition 1500 ppm NO, 1500 ppm C3 H8 , 5 vol.% O2 ,
ature (425 ◦ C), the single-component Co/Al2 O3 and space velocity = 36,000 cm3 gcat −1 h−1 . Enumeration according
Ag/Al2 O3 samples reveal higher reductant selectivi- to Table 1. Some numbers are omitted for clarity. Dotted lines
ties than 20% at high NOx conversions. Furthermore, indicate a 1:1 stoichiometry.
276 M. Richter et al. / Applied Catalysis B: Environmental 36 (2002) 261–277
reveals the lowest degree of propane utilization. The
conclusion is drawn that copper does not provide a
balanced oxidation activity but preferentially oxidizes
propane. Combining Cu with increasing amounts of
Ag (catalyst nos. 55, 52, 46, 36) improves the utiliza-
tion of propane at 475 ◦ C, accompanied by higher NOx
activity. If the Ag content surmounts the Cu content
(catalysts nos. 46, 36), the behavior of the samples re-
sembles more that of the Ag/Al2 O3 single-component
catalyst. Poor efficiency of NOx conversion is
observed for In-containing catalyst formulations.
The single-component In/Al2 O3 catalyst (no. 16) and
the 0.8 In/0.2 Ag combination (catalyst no. 17) have
the lowest NOx conversion of the catalyst library with
a propane utilization at the average 1:1 level.
4. Conclusions
Multi-component catalysts suitable for the SCR
of NOx by hydrocarbons under lean conditions have
been prepared by combination of non-platinum group
metals known for their activity as single-component
supported catalysts. For four elements chosen, a
systematic combination with six concentration in-
crements resulted in a 56 member catalyst library,
that could be screened for the catalytic performance
by high-throughput testing facilities in a short time.
It was shown that synergistic effects are existent in
the multi-component catalyst compositions yielding
high NOx conversions at 450 ◦ C and negligible N2 O
by-product.
Up to the metal loading of 0.5 mmol g−1 , the alu-
mina support prevents formation of crystalline bulk
oxides detectable by XRD although the binding en-
ergies found by XPS point to the existence of In
and Cu in a bulk-like oxide environment equiva-
lent to In2 O3 and CuO, respectively. Cobalt forms a
spinel-like structure, thus, becoming incorporated into
the alumina bulk. Silver is present in form of metallic
nano-sized clusters and Ag2 O according to character-
ization data. The existence of isolated Ag+ ions could
not unambiguously be verified. The findings are rec-
oncilable with literature data [32,33] that silver load-
ing on alumina supports around 2 wt.% or lower leads
to stabilized Ag+ ions, whereas at higher loading,
the existence of Ag clusters is predominant. It can be
estimated that the loading of 0.5 mmol g−1 (5.0 wt.%
Ag) is not an optimum. Nevertheless, a combination
of silver and cobalt is beneficial for the reaction. This
may partly be attributed to the ability of the CoAl2 O4
phase to convert propane to propene which is the
more favorite reductant in the deNOx process.
The utilization of the propane for NOx reduction
seems to be confined to a stoichiometry of 1:1 notwith-
standing other stoichiometries that can be formulated.
Correspondingly, the degree of reductant utilization
varies between 20 and 50%.
To achieve further improvements of the deNOx
activity, one of the less promising components, say
copper, can be replaced by another element. It is ex-
pected that a tri-component catalyst formulation can
be identified with improved catalytic properties.
The main advantage of the performed stage II
screening (optimization mode) is the comparability to
technical unit operations and the higher information
depth of the analyses providing various selectivity
parameters relevant for the deNOx process.
Acknowledgements
Financial support by the Senate of Berlin and the
BMBF (FKZ 03C30120) is gratefully acknowledged.
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