Applied Catalysis A: General 307 (2006) 156–164

www.elsevier.com/locate/apcata

Nature of active sites in decane-SCR-NOx and NO decomposition

over Cu-ZSM-5 zeolites
Jiřı́ Dědeček, Libor Čapek, Blanka Wichterlová *
J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, CZ 182 23 Prague 8, Czech Republic

Available online 2 May 2006

Abstract
Decane-SCR-NOx in the presence of water vapor and NO decomposition were investigated over Cu ions exchanged in ZSM-5 zeolites with
various Si/Al and Al distribution. The local environment of the Cu ions in cationic sites was characterized by the combination of 29Si MAS
NMR, Vis–NIR spectroscopy of Cu(II) ions, Cu(I) Vis emission spectroscopy and UV–Vis spectroscopy of Co(II) ions as probes for the
presence of Al pairs in the framework. The Cu(II) ions coordinated to four framework oxygens of the a- or b-type cationic sites containing Al-
O-(Si-O)2-Al sequences represent the most active sites in decane-SCR-NOx. On contrary, the Cu(I) ions coordinated to two or three framework
oxygens and located at the channel intersection adjacent to the single Al atoms in the a- or b-site control predominantly reaction of NO
decomposition.
# 2006 Elsevier B.V. All rights reserved.

Keywords: NO decomposition; SCR-NOx; Cu-ZSM-5; Al distribution

1. Introduction [5]. However, we have recently reported rather stable and

Since the Iwamoto’s discovery of the high and stable activity
of Cu-ZSM-5 in NO decomposition [1], and pioneering reports
on the Cu-zeolite activity in selective catalytic reduction of NOx
with hydrocarbons (CH-SCR-NOx) [2–4], numerous studies
attempt to analyze the structure of Cu centers and their activity
in these reactions, moreover, by using of various olefins and
paraffins as reductants (see, e.g., Refs. [5–14]). Among these
studies Adriano Zecchina’s group contributed substantially to
analysis of the structure and behavior of Cu ions in zeolites by
applying, besides FTIR, especially XANES and EXAFS
techniques [7,9–11].
Clearly, application of NO decomposition at lean exhaust gas
over Cu-ZSM-5 can hardly be achieved due to high concentration
of oxygen and water vapor in exhaust gas, both poisoning the
active Cu(I) site. Also application of Cu-zeolites in CHx-SCR-
NOx technology was generally questioned by pointing out to their
rather low structural stability, particularly in wet atmosphere,
with respect to the Cu active centers and framework aluminum
* Corresponding author. Tel.: +420 2 6605 3595; fax: +420 2 858 2307.
E-mail address: wichterl@jh-inst.cas.cz (B. Wichterlová).
satisfying activity for reduction of NOx with decane over Cu-
ZSM-5 at lean conditions simulating exhaust gases of diesel
engines, i.e. in an oxygen rich atmosphere (6%), high
concentration of water vapor (12%) and temperature window
250–450 8C [15]. The high activity maintained in time-on-
stream was supposed to be owing to cracking of decane to low
chain olefins, which (and their oxidized or nitrated products)
were strongly bound on the catalyst surface, and thus prevented
molecules of water to be preferentially adsorbed on the active
sites [16]. On contrary, when propane was used as reductant
instead of decane, the SCR-NOx activity of the Cu-ZSM-5 zeolite
dramatically decreased under the presence of water vapor in the
reactant mixture [16].
However, besides an important coordination of the Cu ions,
ZSM-5 zeolites (like other pentasil ring zeolites) represent
silicon rich material (Si/Al > 12), which might possess variety
of distribution of framework aluminum, controlled by the
conditions of hydrothermal synthesis [17,18]. Distribution of
Al atoms in the framework, controlling thus distribution of
negative framework charge affects understandably properties of
metal ion species adjacent to these local Al sequences in
zeolites [13,14,19]. While determination of the distribution of
Al in high silica zeolites is still not satisfactorily solved, it has

0926-860X/$ – see front matter # 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2006.03.017
 J. Dědeček et al. / Applied Catalysis A: General 307 (2006) 156–164 157

been well proven that metal ion species (like, e.g. Cu, Co, Fe) of
various types and location exhibit different (and unusual
coordination), accessibility, reducibility, interactions with guest
molecules as well as catalytic activity (see, e.g., Refs. [20–33]).
However, although that there has been put a lot of effort in
the studies on the Al siting in silicon rich zeolites by using 27Al
MAS NMR [34,35], the problem of determination of Al siting
in these zeolites remains open. We attempt to contribute to the
Al siting in ZSM-5 zeolite framework by using siting of ‘‘bare’’
Co(II) ions in completely exchanged Co-ZSM-5 zeolites as
probes for framework rings of cationic sites, containing two Al
atoms and forming Al-O-(Si-O)1,2-Al pairs [36,37]. It has
further been shown that the conditions of synthesis of zeolites
considerably affect the resulting framework Al distribution
[17,18,38,39].
This paper attempts to bring some more light into
understanding of the activity of Cu ions implanted in cationic
sites of ZSM-5 zeolites in decane-SCR-NOx and NO
decomposition. The emphasis is given here to the effect of
local negative charge balancing the counter cation, controlled
by Al distribution in the framework. The study provides
structural analysis of Cu-ZSM-5 of varying Si/Al/Cu composi-
tion with respect to the location of Cu ions and their charge
balance in the framework ring of cationic site by one or two
aluminum atoms. Such analysis is used for a comparison of Cu
active centers functioning in NO decomposition and decane-
SCR-NOx. The structural analysis of Cu centers and their
surroundings is based on the Cu(II) UV–Vis and Cu(I) emission
spectroscopy. The characteristic spectra of ‘‘bare’’ Co(II) ions
completely exchanged in cationic sites of ZSM-5 zeolites were
used to indicate framework rings containing Al pairs. This
information complemented by 29Si MAS NMR spectra
provided a picture on the distribution of aluminum in the
framework.
2. Experimental
2.1. Preparation of catalysts
Na-ZSM-5-I (Si/Al 13.2) and Na-ZSM-5-II (Si/Al 13.8)
were kindly provided by the Research Institute of Inorganic
Chemistry Inc., Unipetrol, Na-ZSM-5-III (Si/Al 22.5) by the
Institute of Oil and Hydrocarbon Gases, Slovnaft. Cu-ZSM-5-I,
-II and -III zeolites, prepared by Cu(II) ion exchange of the
parent zeolites with diluted solutions of copper acetate at RT,
and Co-ZSM-5-I, -II and -III with maximum level of Co(II) ion
exchange, prepared by ion exchange with 0.05 M Co(NO3)2
solution at RT to prevent formation of cobalt-oxo species, were
those samples preparation of which was already reported in
Ref. [15]. Ca-ZSM-5-I was prepared by ion exchange of Na-
ZSM-5 with 0.5 M Ca(NO3)2 at RT followed by Cu(II) ion
exchange with Cu acetate solution to obtain CuCa-ZSM-5-I.
Chemical compositions of parent and Cu-, Co-, and CuCa-
ZSM-5 zeolites are given in Table 1.
2.2. Spectral characterization of catalysts
UV–Vis–NIR spectra of the as prepared hydrated Cu- and
Co-zeolite samples and of the dehydrated Co-zeolites were
recorded using a Perkin-Elmer UV–Vis–NIR spectrometer
Lambda 19 equipped with a diffuse reflectance attachment with
an integrating sphere coated by BaSO4. BaSO4 was also used as
a reference, see Refs. [16,37].
Prior to monitoring of the Cu(I) photoluminescence
spectrum, the Cu(II) zeolite was dehydrated and subsequently
reduced for 1 min in hydrogen at temperature of 250 8C, i.e. at
conditions to achieve maximum concentration of the mono-
valent copper and then evacuated; details for the procedure
leading to reduction of divalent to monovalent copper were

Table 1
Chemical composition of parent and Cu-, CuCa and Co-ZSM-5 zeolites (on dry basis), distribution of Al and Cu species and N2 yields in decane-SCR-NO at 250 8C
and NO decomposition at 400 8C
Zeolite Si/Al Cu/Al Ca/Al Co/ 2Ala (Cu2Al)/ ðCu1Al Þ/ Cu2Ald Decane-SCR-NO NO decomposition
AlMAX rel. (%) AlMAX b AlMINc rel. (%) N2 yield (%) N2 yield (%)
Na-ZSM-5-I 13.2 – – 0.22 44 – – – – –
Cu-ZSM-5-I 13.2 0.06 – – – – – – 13.3 0.2
Cu-ZSM-5-I 13.2 0.07 – – – – – – 11.0 –
Cu-ZSM-5-I 13.2 0.17 – – – – – – 14.3 1.7
Cu-ZSM-5-I 13.2 0.35 – – – – 0.13 – 17.9 8.9
Cu-ZSM-5-I 13.2 0.45 – – – 0.22 0.23 49 30.9 17.1
Cu-ZSM-5-I 13.2 0.48 – – – 0.22 0.26 46 16.5 –
Cu-ZSM-5-I 13.2 0.50 – – – 0.22 0.28 44 24.2 18.8
Cu-ZSM-5-I 13.2 0.58 – – – 0.22 0.36 40 32.4 –
Cu-ZSM-5-I 13.2 0.63 – – – 0.22 0.41 35 25.3 –
CuCa-ZSM-5-I 13.2 0.21 0.04 – – – 0.03 – 6.3 –
Na-ZSM-5-II 13.8 – – 0.20 40 – – – – –
Cu-ZSM-5-II 13.8 0.67 0.67 – – 0.20 0.47 30 24.1 –
Na-ZSM-5-III 22.5 – – 0.11 22 – – – – –
Cu-ZSM-5-III 22.5 0.44 0.44 – – 0.11 0.33 25 7.0 19.2
a
2Al = (2
Co/AlMAX)/1
100.
b
CuMAX
2Al /Al = Co/AlMAX.
c
CuMAX
2Al /Al = Cu/Al  (Cu2Al)/AlMAX.
d
Cu2Al = (Cu2Al/AlMAX)/(Cu/Al)
100.
158 J. Dědeček et al. / Applied Catalysis A: General 307 (2006) 156–164

published elsewhere [19,40]. Cu(I) sample was excited by the

XeCl excimer laser (Lambda Physik 205, emission wavelength
308 nm). The emission spectrum was recorded using a laser
kinetic spectrometer (Applied Photophysics) and processed by
a computer (details, see in Refs. [22,40]).
Single pulse and cross-polarization 29Si MAS NMR spectra
of parent Na-ZSM-5 zeolites were recorded on a Bruker Avance
500 MHz (11.7 T) Wide Bore spectrometer operating at
Larmor frequency 99.35 MHz using 4 mm o.d. ZrO2 rotors
rotated at 5 kHz, as described in Ref. [27].

2.3. Catalytic tests

Selective catalytic reduction of NO with decane and NO

decomposition were carried out at GHSV of 30,000 and
15,000 h1 in a quartz through flow micro-reactor at a total
flow rate of 150 ml min1. Typical reactant mixture at decane-
SCR-NOx and NO decomposition consists of 1000 ppm NO,
450 ppm C10H22, 6% O2, 12% H2O in He and 4000 ppm NO in
He, respectively. Concentrations of NO and NO2 were monitored
by an NO/NOx chemiluminescence analyzer (Horiba) enabling
to analyze NO and NO2 in high concentration of water vapor in
the stream. Concentrations of CO2, CO, N2 and N2O were
provided by an on-line connected gas chromatograph Hewlett-
Packard 6090. For more details, see Ref. [27]. Fig. 1. 29Si MAS NMR spectrum (a), its simulation (b), Gaussian bands
corresponding to individual resonances (c; dashed lines) and 29Si CP MAS
3. Results NMR spectrum (d) of the as-prepared Na-ZSM-5-I.

3.1. Distribution of Al-O-(Si-O)1,2-Al sequences and single
Al atoms in the framework
29
Si MAS and CP MAS NMR spectra of Na-ZSM-5-I, shown
in Fig. 1, are similar to those reported for other ZSM-5 zeolite
samples in Ref. [34]. Four resonances at 101.2, 106.5,
109.4, 113.0 and 116.9 ppm can be identified in the MAS
NMR spectrum, as follows from its simulation. Resonances at
113.0 and 116.9 ppm correspond to two groups of Si(4Si)
atoms with different average Si–O–Si bond angles. Resonances
centered at 106.5 and 109.4 can be attributed to two groups of
Si(1Al, 3Si) atoms. Resonance at 101.2 ppm is in the region,
where the resonance might correspond to both Si(2Al, 2Si) and
Si(OH) entities. A significant increase of the 101.2 ppm
resonance intensity with the CP experiment suggests attribution
of this resonance to the Si(OH) atoms. Si/AlNMR value of ZSM-5-
I was estimated using relation Si/AlNMR = I/0.25 I1Al, where I is
the total intensity of 29Si MAS NMR spectrum and I1Al
corresponds to the intensity of resonance of Si(1Al, 3Si) atoms.
The obtained value of Si/AlNMR = 13.5 is in a good agreement
with the Si/Al value obtained from chemical analysis (Si/
Al = 13.2). This finding confirms the above given attribution of
the individual resonances of the 29Si MAS NMR spectrum.
The overall concentration of close framework Al atoms can
be determined by using concentration of Co(II) ions in
completely exchanged Co-ZSM-5 with respect to ‘‘bare’’
divalent cations. Maximum ion exchange capacity of the zeolite
for Co(II) hexaquacomplex equals concentration of close Al
atoms in the framework. This value, expressed as Co/AlMAX,
for the individual zeolites is given in Table 1. The differences in
the maximum Co(II) ion exchange capacity (Co/AlMAX 0.11–
0.22) reflect different content of aluminum pairs in the
framework of parent zeolites. Thus, from 22 to 44% of Al atoms
in the studied zeolites belong to Al pairs located in one ring and
forming cationic site or close unpaired Al atoms (Al atoms
close enough to balance Co(II) hexaaquacomplex, but not
located in one framework ring). UV–Vis spectroscopy of
dehydrated maximum exchanged Co-zeolites enables to
distinguish between these two types of close Al atoms. d–d
transitions of the Co(II) ions in Vis region correspond to ‘‘bare’’
Co(II) ions in cationic sites balanced by Al pairs located in one
ring of these sites, while the broad charge transfer band around
33,000 cm1 of O-bridging Co species reflects presence of
close unpaired Al atoms in the framework; for details, see Refs.
[36,37]. Only bands belonging to d–d transitions of Co(II) ions
are present in the Vis region of the spectrum of dehydrated Co-
ZSM-5-I (Fig. 2). Thus, concentration of close unpaired Al
atoms in the framework is negligible and only Al pairs (22–44%
of Al atoms) and single Al atoms (78–56% of Al atoms) are
present in the frameworks of the zeolites investigated here.
Note that absorption coefficient of Co O-bridging species is
several magnitudes higher compared to those of ‘‘bare’’ Co(II)
ions. The decomposition of the Vis spectrum to the Gaussian
bands fit well with the seven bands in the spectrum, ascribedin
Co-ZSM-5 zeolites to the Co(II) ions in the a-, b- and g-type
cationic sites. The bands attribution was made by using Co-
zeolite samples containing prevailing one type of the Co ions
(for details, see Ref. [41]). Moreover, the quantitative analysis
 J. Dědeček et al. / Applied Catalysis A: General 307 (2006) 156–164
Fig. 2. Vis spectrum of dehydrated Co-ZSM-5-I (a), its simulation (b) and
Gaussian bands corresponding to the Co(II) ion in the a-site (—), b-site (- - -)
and g-site () (c).
of the spectrum using absorption coefficients, given in Ref.
[41], enabled to estimate concentration of Al pairs in the
individual types of sites.
3.2. Cu ions in cationic sites with single Al atoms and Al
pairs
Changes in the relative concentration of Cu ion sites
adjacent to one or two framework aluminum atoms can be
followed up by the changes of the position of the high-energy
edge in the Vis–NIR spectra of the Cu(II) ion in the Cu-ZSM-5
zeolites, as described in Ref. [42]. In our previous study, we
reported (Fig. 3; Ref. [16]) the shift of the high-energy edge of
the broad absorption band with maximum at 12,500–
13,000 cm1 to higher frequency with increasing Cu loading
for Cu-ZSM-5 zeolites. The shift of the high-energy edge of the
Cu(II) absorption band indicates the increasing relative
concentration of monovalent [Cu2+(H2O)5X]+ complexes in
the zeolite with X like OH or acetate group. These complexes
are suggested to be located in the vicinity of single framework
aluminum atoms, which cannot be balanced by divalent
complexes.
There is no method available to quantify the distribution of
Cu(II) ions located in the vicinity of one or two Al atoms.
Nevertheless, this distribution can be suggested for low or high
loaded samples according to the following consideration. At the
lowest Cu loading, the shift of the absorption edge is negligible
and all Cu(II) ions can be suggested to be located in the vicinity
of two framework Al atoms. In the case of high loaded Cu-
zeolites, maximum possible loading of Cu ions in the vicinity of
159
Fig. 3. Normalized Vis–NIR spectra of the as-prepared Cu-ZSM-5-I zeolites
with Cu/Al 0.06 (- - -), 0.58 (——). Peak at 7 120 cm1 corresponds to
combination vibration band of OH groups, and the band at 10,720 cm1 is
an instrument artifact. Dependence of the position of high-frequency edge of
Cu2+ band in as-prepared Cu-ZSM-5-I on Cu loading.
two framework Al atoms (Cu2Al) is given by the concentration
of Al pairs forming cationic sites. Note that Cu(II) ions are
preferentially exchanged in the vicinity of two Al atoms [42].
The concentration of Al pairs in the investigated zeolites
corresponds to the maximum of their Co(II) exchange capacity.
Thus, maximum concentration of Cu(II) ions in the vicinity of
two Al atoms, (Cu2Al)/AlMAX corresponds to maximum Co(II)
ion exchange capacity Co/AlMAX. The rest of the Cu ions have
to be exchanged adjacent to the single AlO2 framework
entities. Thus, Cu1Al/Al = Cu/Al  Co/AlMAX for the highly
Cu-loaded samples. The suggested distribution of Cu1Al and
Cu2Al in the investigated Cu-ZSM-5 samples is given in
Table 1.
3.3. Cu(I) luminescence
Cu(I) emission spectrum of Cu-ZSM-5-III-0.44 (the sample
pre-reduced to reach maximum concentration of Cu(I), see
Refs. [20,40]) corresponds to those reported for Cu-ZSM-5
zeolites [20,22,24,40,43,44]. It is formed by two main emission
bands centered at 480 and 545 nm, as depicted in Fig. 4. A
shoulder around 610 nm is an artifact due to laser excitation at
308 nm. Both bands correspond to single Cu(I) ions located in
extra-framework sites of ZSM-5 [20,22,24,40] that will be in
the following defined as Cu480 and Cu545, respectively. Decay
times of 480 and 545 nm emissions at 55 and 120 ms were
already reported [40]. Emission intensity of the Cu(I) samples
with integrated time from t = 0 to 1 can be used as a measure
of the concentration of the individual Cu(I) emission centers
[22,40,45]. The Cu480 centers represent ca. 40% and Cu545
centers ca. 60% of Cu ions in the ZSM-5-III-0.44.
3.4. Catalytic activity
NO was converted exclusively to molecular nitrogen and
oxygen over Cu-ZSM-5 zeolites in the reaction of NO
decomposition. With the increasing Cu loading increased N2
160 J. Dědeček et al. / Applied Catalysis A: General 307 (2006) 156–164
Fig. 4. Cu(I) emission spectrum (a), its simulation (b) and Gaussian bands
corresponding to individual emission bands (c; dashed lines) of Cu-ZSM-5-III-
0.44 reduced for 1 min in hydrogen at 250 8C recorded at 5 ms after excitation
pulse.
yield (Table 1). High activity of Cu-ZSM-5 zeolite samples in
decane-SCR-NO under water vapor presence has already been
reported elsewhere [15,16]. At GHSV 30,000 h1 the conver-
sion of NO to N2 reached maximum value (58%) at 300 8C;
NOx was converted mainly to N2 (>95%). Formation of NO2
appeared above 350 8C, when decane was completely
consumed. Only trace concentration of N2O, i.e. up to max
5 ppm, was found. Data on decane-SCR-NOx and NO
decomposition over Cu-zeolites are summarized in Table 1.
To analyze the complex Cu-ZSM-5 system in decane-SCR-
NO and NO decomposition the turn-over-frequency values for
NO-N2 transformation per Cu ion (TOF) were used. TOF values
were compared at 250 8C for decane-SCR-NOx, i.e. well below
the maximum of N2 yield, and at 400 8C for NO decomposition
(Fig. 5). While the TOF values per one Cu ion significantly
decreased with the increasing Cu loading in decane-SCR-NO,
they increase with the increasing Cu loading in NO
decomposition. A single-exponential dependence of TOF
values with Cu loading suggests the presence of two different
Cu centers in the zeolite. One is occupied preferentially at low
Cu loading and is responsible for higher activity in decane-
SCR-NO and the second one, populated at higher Cu loadings,
exhibits dominant activity in NO decomposition.
Fig. 5. Dependence of TOF (h1) on Cu loading in C10H22-SCR-NO under
water presence at 250 8C and in NO decomposition at 400 8C over Cu-ZSM-5-I.
4. Discussion
4.1. Nature and distribution of Cu ions in Cu-ZSM-5
In general, single Cu ions in cationic sites adjacent to one or
two framework Al atoms, Cu–O–Cu entities or Cu  Cu pairs,
small CuxOy clusters or CuO particles have been reported to be
present in Cu-zeolites [32,33,46]. Nevertheless, we have
already shown that the Cu-zeolites with highly prevailing Cu
ions exchanged in cationic sites can be prepared by careful Cu
ion exchange [21,30]. Moreover, the UV–Vis–NIR spectrum of
the hydrated sample and of that sample hydrated after the
catalytic test exhibits exclusively absorption band correspond-
ing to aquocomplexes of Cu(II) ions (not shown in figure). It
indicates that formation of oxide like Cu species, exhibiting
absorption in the Vis region [13,19], can be excluded in the as
prepared samples as well as under reaction conditions; for
details, see Ref. [30]. The presence of Cu–O–Cu entities were
reported only for the ‘‘over-exchanged’’ Cu-zeolites [21,47,48]
and not for Cu-ZSM-5 with Cu/Al  0.5 [25,46,47,49]. Thus,
only the structure and behavior of di- and monovalent
atomically dispersed, single Cu ions in cationic sites will be
discussed.
NIR–Vis spectroscopy of Cu species in hydrated Cu-ZSM-5
zeolites was suggested for analysis of local framework charge
in the surrounding of Cu(II) ions in zeolites. Two types of Cu
ions were reported for Cu-ZSM-5 [42]. At low Cu loadings,
Cu(II) ions were located predominantly in vicinity of two
framework Al atoms. With increasing Cu loading, Cu(II) ions
adjacent to single Al atoms were formed. Formation of the
latter Cu(II) ions in hydrated zeolites was evidenced by the shift
of the high-energy edge of the complex Cu(II) absorption band
centered around 12,000 cm1. Thus, as follows from the
spectra of the hydrated zeolites (see Fig. 3) and the dependence
of the corresponding positions of high-energy edge of Cu(II)
band, both types of the Cu(II) ions, i.e. those located in vicinity
of one and two Al atoms, were present in the Cu-ZSM-5-I
catalysts.
There is no doubt that Al local density in cationic sites
affects behavior of transition metal ions [13,14,19,27]. The
indirect method employing siting of ‘‘bare’’ Co(II) ions
(monitored via Vis spectroscopy) was developed to estimate
concentration of Al pairs (Al-O-(Si-O)1,2-Al sequences)
located in zeolite rings of cationic sites [36,37]. Exclusive
presence of Al-O-(Si-O)2-Al pairs can be suggested in the
investigated samples, because the Si(2Al, 2Si) local structures
in the framework of ZSM-5-I can be excluded according to the
29
Si MAS NMR experiment (see Fig. 1). The presence of such
arrangement in the ZSM-5-II and -III zeolites was also not
observed (not shown in figure).
As for the distribution of Al atoms in ZSM-5-I, -II and -III,
there was about 44, 40 and 22% of aluminum, respectively,
located in Al pairs, as follows from the degree of maximum
Co(II) ion exchange of the corresponding zeolites (Table 1). At
low Cu loadings, the Cu ions are exchanged preferentially in the
vicinity of two framework Al atoms. Thus, presence of Cu ions
balanced by a single AlO2 framework entity can be neglected
 J. Dědeček et al. / Applied Catalysis A: General 307 (2006) 156–164
Fig. 6. Illustration of the cationic sites for divalent cations in ZSM-5 structure
according to Ref. [41].
for Cu/Al < 0.1. All Cu(II) ions can be supposed to belong to
those in the vicinity of Al pairs. For the highly Cu loaded
samples, where the degree of the Cu ion exchange is
significantly higher than is the zeolite capacity for Cu(II) ions
in the vicinity of Al pairs, the complete occupation of the sites
formed by Al pairs can be supposed. In this case, the difference
between the Cu concentration and maximum capacity for
Cu(II) ions in vicinity of Al pairs can be taken as concentration
of Cu(II) ions in the vicinity of single Al atoms (Table 1). Note
that the Cu loading even in the high loaded Cu samples does not
exceed zeolite ion exchange capacity under the assumption that
one Cu ion is located in the vicinity of single Al atom or Al pair.
Thus, location of two Cu ions in cationic sites containing two
Al atoms in the ring, resulting in the formation of Cu pairs, can
be neglected.
Application of Co(II) ions as probes enables not only to
estimate concentration of Al pairs in cationic sites, but also
distribution of Al pairs among rings forming individual cationic
sites for divalent cations [36,37]. With ZSM-5 three cationic
sites denoted as a-, b- and g-sites were suggested from the
Co(II) UV–Vis and FTIR spectroscopy [30,41] (see Fig. 6). The
Fig. 7. Illustration of siting and coordination of the Cu(II) ion active in decane-SCR-NO (A) and Cu(I) ion active in NO decomposition (B).
161
a-site is located in the main channel and represents two five-
member rings forming the six-member ring on the channel wall.
Because Al-O-Si-O-Al pairs are not present in the investigated
ZSM-5 frameworks, two Al atoms in the a-site are suggested to
be located at T2 and T11 or T5 and T8 sites. The b-site is
located on the channel intersection and it is formed by six-
member ring. Al pairs can be located in T1 and T7, T4 and T10
or T5 and T11 sites. A complex boat-shaped g-site is located in
the sinusoidal channel and cations located in this site represent
minority in ZSM-5. Both three sites are present in ZSM-5-I, as
follows from the Vis spectra decomposition illustrated in Fig. 2.
In parallel with Co(II) siting in ferrierite obtained from XRD
experiment [50,51] (note that similar siting of Co(II) ion in the
a-site was suggested for ferrierite and ZSM-5 according to
UV–Vis–NIR study [41] and according to the theoretical model
of Cu(II) siting in ZSM-5 [26], following coordination of Cu(II)
ion can be suggested. The Cu(II) ion in the a-site is located
above the plane of six-member ring formed by two five-
member rings and coordinated to four framework oxygens with
Cu(II)-O distance around 0.2 nm. Cu(II) ion is on the top of
pyramid with the base formed by the oxygens. The Cu(II) ions
in the b-site are located in the center of six-member ring near
ring plane and coordinated to four framework oxygens. Siting
of Cu(II) ions is schematically depicted in Fig. 7A.
In the case of Cu(I) ions, these ions can be monitored via
emission spectroscopy [20–22,24,40,44]. However, this
method is sensitive only to the local environment of the
excited Cu(I) ion and does not reflect the geometry of the ring
accommodating Cu(I) ion or number of Al atoms in the ring.
The reason is that the excited Cu(I) ion is always coordinated to
two framework oxygens neighboring Al atom [26,50,51]. With
Cu-ZSM-5, the Cu(I) ions located at the channel intersection
were attributed to the Cu545 center while Cu(I) ions located in
the wall of the main channel were attributed to the Cu480
emission center. Thus, this method can be employed to monitor
Cu siting in the zeolite channel system.
As illustrated in Fig. 4, emission band at 545 nm dominates
the spectrum of Cu(I)-ZSM-5-III-0.44. This agrees well with
the relative increase of the concentration of the Cu545 emission
center with increasing Cu loading and decreasing framework
162 J. Dědeček et al. / Applied Catalysis A: General 307 (2006) 156–164

aluminum content in ZSM-5 reported elsewhere [20,22,40]. Table 2

N2 yields and TOF values in decane-SCR-NO at 250 8C over Cu- and CuCa-
The concentration of the Cu480 emission centers of ca. 40 rel.%
ZSM-5-I
for the zeolite with Cu/Al 0.44 is significantly higher compared
to the concentration of Cu(II) ions in the vicinity of two Al Zeolite Cu/Al Ca/Al N2 yield (%) TOF (h1)
atoms (ca. 25 rel.% for this sample). Thus, the Cu480 emission Cu-ZSM-5-I-0.17 0.17 – 14.3 2.1
center cannot be identified with Cu(I) ions located in the CuCa-ZSM-5-I 0.21 0.04 6.3 0.7
vicinity of two Al atoms and the Cu545 emission center with the Cu-ZSM-5-I-0.35 0.35 – 17.9 1.3
Cu(I) ions in vicinity of single Al. This is in agreement with the
nature of Cu(I) emission in zeolites suggested by Nachtigallová
et al. [26,52]. It follows that the Cu545 emission center suggested to be responsible for the most decane-SCR-NO
corresponds to the Cu(I) ions located in the vicinity of a single activity. The second one is formed at higher Cu loadings and
Al atom at the channel intersection. possesses low activity. It has to be noticed that Cu(II) ions
Recently, we have reported indirect method employing of Li adjacent to Al pairs are more resistant to reduction to Cu(I) ions
ions monitored via 6,7Li MAS NMR for the characterization of in contrast to those adjacent to single Al atoms [20,22]. It
Al atoms in the structure of ZSM-5 [53]. Three resonances implies that the divalent Cu ions balanced by Al pairs in the ring
around 0.6, 0.3 and 0.0 ppm were observed in the 6Li and of the cationic sites are the centers highly active in SCR-NOx.
7
Li MAS NMR spectra of ZSM-5. Each resonance corresponds Attribution of the activity in decane-SCR-NO to Cu ions
to the Li ion in specific environment–cationic site. NMR balanced by Al pairs was further confirmed by the effect of co-
spectra of the individual samples differed in the intensity of the cation presence on the activity of the CuCa-ZSM-5-I zeolite.
observed resonances, but the chemical shift of the observed Ca(II) ions are exclusively exchanged at cationic sites with Al
resonances was not affected by the concentration of Al pairs in pairs. Thus, the presence of Ca ions in CaCu-ZSM-5 decreases
the zeolite. It indicates that single Al atoms are located in ZSM- concentration of the Cu ions in cationic sites with Al pairs. This
5 framework at the same T sites as Al atoms belonging to Al decrease in concentration of the suggested active Cu-species
pairs. This enabled, between others, to suggest cationic sites of results in N2 yield and TOF values significantly lower for
ZSM-5 matrix containing single Al atom and accommodating CuCa-ZSM-5-I in comparison with Cu-ZSM-5-I both contain-
only monovalent cations. Note that parent zeolites used for the ing similar Cu content; (see Table 2). Moreover, the TOF
preparation of Cu-catalysts were employed also for the 6,7Li related to the Cu(II) ion adjacent to the Al pairs ðTOF Cu2Al Þ
MAS NMR study. Thus, conclusions made on siting of gives similar values for all high Cu exchanged zeolites
monovalent cations and single Al atoms in the ZSM-5 independently on the total concentration of Cu ions and
framework can be used to suggest siting of Cu(I) ions located framework aluminum (Table 3).
in the vicinity of single Al atom. Only Al atoms in the T2 and It can be concluded that the Cu(II) ions located in ZSM-5
T5 site of the a-site are located in the channel intersection and zeolite in the a- and b-sites containing Al-O-(Si-O)2-Al pairs
can accommodate Cu(I) ion with emission at 545 nm. In the exhibit high activity in decane-SCR-NO. These active sites are
case of the b-site, all atoms are located in the channel schematically depicted in Fig. 7A.
intersection, but only Cu(I) ions balancing Al atoms in T1 and
T5 site can be attributed to the Cu545 emission center. Cu(I) ions 4.3. Nature of the reaction center for NO decomposition
belonging to all other Al atoms of the b-site exhibit less open
environment where long wavelength of the Cu(I) emission can Cu-ZSM-5 (and other high silica zeolites) represents a
be excluded. unique catalytic system regarding the NO decomposition.
Coordination of Cu(I) or Cu(II) ions in ZSM-5 with Si/Al Nevertheless, there is still a discussion on the structure of the
25–35, where predominating single Al atoms can be supposed, active Cu species. There is general agreement that monovalent
was investigated by Lamberti et al. by EXAFS [24,46]. Cu ion species are involved in the reaction. However, both
Coordination of Cu(I) ion to two framework oxygens and of single Cu(I) ions and Cu(I)  Cu(I) bridging species have been
Cu(II) ions to two or three oxygens was suggested. Thus, suggested to represent the active centers in NO decomposition,
prevailing Cu(I) ions are located in Cu-ZSM-5-III-0.44 in the see, e.g., Refs. [6,12,13,22,54,55].
channel intersection and coordinated to two framework
oxygens of neighboring Al atoms in T2 and T5 sites of the Table 3
a-site or T1 and T5 site of the b-site. Cu(II) ions are located in TOF in decane-SCR-NO at 250 8C and that related to Cu ions adjacent to Al
the vicinity of the same Al atoms and coordinated to two or pairs for Cu-ZSM-5 zeolites
three framework oxygens (see Fig. 7B). Zeolite Cu2Al N2 yield TOF TOFCu2Al
(%) (%) (h1) (h1)
4.2. Nature of the reaction center for decane-SCR-NOx Cu-ZSM-5-I-0.45 49 30.9 1.68 3.3
Cu-ZSM-5-I-0.50 44 24.2 1.19 2.6
Referring to the discussion above and results reported Cu-ZSM-5-I-0.58 40 32.4 1.36 3.5
previously, two types of Cu species of different activity in Cu-ZSM-5-I-0.63 35 25.3 1.15 3.0
Cu-ZSM-5-II-0.67 30 24.1 1.10 2.9
decane-SCR-NO were reported previously [16]. The first Cu Cu-ZSM-5-III-0.44 25 7.0 0.77 2.5
species is preferentially formed at low Cu loadings and can be
 J. Dědeček et al. / Applied Catalysis A: General 307 (2006) 156–164
Table 4
TOF in NO decomposition at 400 8C and that related to Cu ions adjacent to
single Al atoms for Cu-ZSM-5 zeolites
Zeolite Cu1Al N2 yield TOF TOFCu2Al
(%) (%) (h1) (h1)
Cu-ZSM-5-I-0.45 51 17.1 0.93 1.9
Cu-ZSM-5-I-0.50 56 18.8 0.92 1.8
Cu-ZSM-5-III-0.44 75 19.2 1.58 2.0
The observed negligible TOF values in NO decomposition
(related to one Cu ion) at low Cu loading, increases sharply at
medium Cu ion exchange degree, as illustrated in Fig. 5 and in
agreement with Refs. [20–22,54,55]. It can be suggested that
the Cu(I) ions located in the vicinity of Al pairs, which
predominate at low Cu loading exhibit low tendency to be
reduced to Cu(I) and thus low activity in NO decomposition.
Maximum loading of these Cu(I) ions equals in Cu-ZSM-5-I to
Cu/Al 0.22 (Table 1), the rest of the Cu(I) ions should be located
in the vicinity of single Al atoms. The increase in the relative
concentration of the Cu ions balancing single Al atoms is
evidenced by the shift of the high-energy edge of the absorption
band of the Cu(II) ion in the as-prepared Cu-zeolites. It suggests
that the activity of Cu-ZSM-5 in NO decomposition is
controlled by the concentration of Cu(I) ions in the vicinity
of single framework Al atoms. The attribution of the NO
decomposition activity to Cu(I) ions in vicinity of single Al
atoms is further supported by the fact that both N2 yield and
TOF values for Cu-MFI-5-III (Si/Al 22.5), containing more
single Al atoms (75%), are significantly higher than those of
Cu-ZSM-5-I-0.45 and -0.50 with 51–56% of single Al atoms,
see Table 4.
Moreover, the TOF related to the Cu(I) ion adjacent to the
single Al atoms ðTOFCu1Al Þ give similar values independently
on the concentration of Al and Cu in the zeolite (1.8–1.9 h1,
Table 4). Note that TOFCu1Al values can be estimated only for
highly loaded Cu-zeolites.
The Cu(I) emission at 545 nm highly prevails in the
spectrum of Cu(I)-ZSM-5-III, exhibiting the highest TOF
value. Thus, this Cu(I) emission center can be attributed to the
active center. This is in agreement with the previously reported
results for Cu-ZSM-5 and Cu-beta zeolites [20–22,30,45]
where emission at 545 nm was suggested as a marker of active
Cu(I) species. Based on the conclusions given above, the
activity of Cu-ZSM-5 catalyst in NO decomposition can be
attributed to the Cu(I) ions coordinated to two or three
framework oxygens neighboring single Al atom in T1, T2 and
T5 framework sites, and located at the channel intersection.
Siting and coordination of these Cu(I) ions is schematically
depicted in Fig. 7B.
The theoretical maximum concentration of Cu(II) ions in
cationic sites of ZSM-5-I is Cu/Al = 0.78, note that the
concentration of Cu(II) ions balancing Al pair is equal to Cu/Al
0.22 (Table 1), and the rest of the Cu(II) ions balances single Al
atoms. Thus, for Cu-ZSM-5-I with Cu/Al  0.50, the
concentration of two Cu(I) ions bound on the Al pairs is
negligible. Note that only such Cu ions could form Cu(II)-O-
Cu(II) or Cu(I)  Cu(I) species in ZSM-5 structure.
163
In the case of over-exchanged Cu-zeolites, where
Cu(I)  Cu(I) species were reported by EXAFS, a declination
of TOF values clearly indicates negligible or significantly lower
activity of these species [19,21,56–58]. Moreover, the highest
NO decomposition activity per Cu ion was found for Cu-
zeolites with high Si/Al ratios and medium Cu loadings
[22,30,45,59]. It implies that the Cu(I)  Cu(I) species can be
rather regarded as the observing species.
4.4. Al distribution in the framework, counter cation
properties and performance in catalysis
As it was discussed above, local Al density in the zeolite
framework substantially affects performance of Cu-ZSM-5
catalyst in SCR-NOx and NO decomposition. The relation
between Al distribution in the zeolite framework and properties
of counter transition metal ions located in the zeolite is not yet
well understood. Nevertheless, some possibilities how Al
distribution affects catalytic performance of metallo-zeolites
can be suggested.
Al local density significantly affects redox properties of the
Cu ions in cationic sites of ZSM-5 and other silicon rich
zeolites. Cu(II) ions located in vicinity of single framework Al
atoms were reported to be easier reduced to Cu(I) compared to
the ions balanced by Al pairs [13,14,20,22]. Thus, monovalent
state can be supposed to be more probable in the case of Cu ions
balancing single Al atoms bearing lower framework negative
charge. Similarly framework Al density affects interaction of
Cu(I)/Cu(II) ions with NO [21,22] and other guest molecules
[24,25]. Other feature affected by the Al local density is the
coordination of Cu(I)/Cu(II) ions as follows from theoretical
modeling of Cu siting in ZSM-5 [26]. In addition, other
parameter, which can be controlled by Al local density are
distances between reaction centers.
Siting of Al atoms in the individual framework T sites also
affects coordination of Cu(I)/Cu(II) ions, as follows from
theoretical modeling [52] as well as their interaction with guest
molecules [60,61].
There is no doubt that Al local density in the so far
investigated ZSM-5 can be significantly varied by zeolite
synthesis or by post-synthetic treatment in a wide range of the
concentration of framework Al [17,18,38,39]. This brings about
a possibility to design ZSM-5 based catalysts with tuned Al
distribution for optimum catalytic performance in the deNOx
and generally in redox processes.
5. Conclusions
The active sites for decane-SCR-NOx and NO decomposi-
tion in Cu-ZSM-5 are represented by different Cu centers, but
both centers represent the exchanged Cu ions with open
coordination sphere coordinated to framework oxygen atoms.
The Cu sites most active in decane-SCR-NO are not
(or negligibly) active in NO decomposition and vice versa.
The properties and activity of Cu centers are controlled by the
distribution of Al atoms in the cationic sites of the zeolite
framework.
164 J. Dědeček et al. / Applied Catalysis A: General 307 (2006) 156–164
The Cu(II) ions exhibiting high activity in decane-SCR-NO
are located in the a- and b-type sites of ZSM-5 structure
containing Al-O-(Si-O)2-Al pairs.
Cu(I) ions active in NO decomposition are located in the
ZSM-5 channel intersection in the vicinity of single framework
Al atom of the a- or b-site.
Acknowledgement
The financial support from the Academy of Sciences of the
Czech Republic through the projects # 1ET400400413 and
IAA4040308 is gratefully acknowledged.
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