Applied Catalysis A: General 281 (2005) 199–205

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Dispersion and surface states of copper catalysts by

temperature-programmed-reduction of oxidized surfaces (s-TPR)
Antonella Gervasini*, Simona Bennici
Dipartimento di Chimica Fisica ed Elettrochimica, Università degli Studi di Milano, via Camillo Golgi, 19, I-20133 Milano, Italy
Received 24 September 2004; received in revised form 22 November 2004; accepted 22 November 2004
Available online 30 December 2004

Abstract

Surface and sub-surface oxidation of dispersed copper phase by N2O adsorptive decomposition at controlled temperature followed by H2
temperature-programmed-reduction of the Cu2O surface layers formed (s-TPR) was performed on siliceous supported catalysts (ca. 6 wt.%
Cu). The combined analysis permitted to measure the copper dispersion and to identify different surface copper species. Copper dispersion
parameters were calculated from the H2-uptakes in the back-titration of the oxygen atoms fixed on the Cu particles by the s-TPR analysis. S-
shaped curves were obtained plotting the H2-uptakes versus N2O oxidation temperature, the change of slope could indicate the beginning of
copper deep oxidation, ca. 70 8C, that continued up to bulk oxidation at higher temperatures. Extrapolation of the H2-uptake to ‘‘zero-
temperature’’ allowed calculating the ‘‘true’’ copper dispersion (D
Cu ) and related parameters. In addition, s-TPR provided qualitative and
quantitative reduction profiles of the copper surface species. Besides Cu2O, formed by N2O oxidation of Cu(0) particles, copper species
strongly interacting with support were clearly individuated as a function of the support nature.
# 2004 Elsevier B.V. All rights reserved.

Keywords: Cu catalysts; Cu dispersion; Cu surface species; N2O oxidation; Temperature-programmed-reduction

1. Introduction it appears that a large debate is continuing from some

Copper catalysts have long been used and are actually
used in many petrochemical processes, such as the water–
gas reaction and methanol synthesis. In the last decade,
copper-containing zeolites and highly dispersed amorphous
copper oxide systems have been extensively studied due to
their exceptional activity in catalytic reactions considered as
potential ways for abatement of major air pollutants, e.g.,
NO decomposition [1–3], selective catalytic reduction of
NOx by hydrocarbons (HC-SCR process) [4,5], and
decomposition of nitrous oxide [6].
The performances of the catalysts are related to the
copper dispersion, DCu, and, therefore, the search for reliable
methods for determining DCu and related parameters
(specific Cu surface area, MSA, and average diameter of
the copper aggregates, Øav) is essential to interpret their
activity in terms of turnover frequencies. From the literature,
* Corresponding author. Tel.: +39 02 50314254; fax: +39 02 50314300.
E-mail address: antonella.gervasini@unimi.it (A. Gervasini).
decades about the most suitable adsorbate to be used for the
Cu dispersion determination through chemisorption meth-
ods [7–14]. The existence of weak reversible chemisorption
and uncertain adsorption stoichiometries is associated with
adsorbates, such as H2 and CO [10,12]. Low-temperature O2
chemisorption (195 or 136 8C) has been proposed as a
reliable technique for the measurement of Cu surface areas
[7,15], although this procedure is very time-consuming. To
overcome this problem, O2 chemisorption at 130 8C
through the pulse flow technique, which should be more
suitable for routine measurements, has been adopted and
recently described by Pernicone et al. [16]. However, O2
chemisorption can be unreliable for catalysts containing low
loadings of copper or for catalysts in which the support is
partially reducible, as pointed out in the paper of Bartley
et al. [17].
The procedure, which involves adsorptive decomposition
of N2O has been used most frequently [8,9,11,14,18,19].
Different operating procedures have been applied to
determine the extent of the reaction of N2O with the surface

0926-860X/$ – see front matter # 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2004.11.030
200 A. Gervasini, S. Bennici / Applied Catalysis A: General 281 (2005) 199–205
copper: volumetric determination of the N2 produced by
freezing out the excess of N2O [9,11], chromatographic
separation of unreacted N2O and N2 formed [8,14],
gravimetric determination of the increasing in weight of the
sample due to oxygen chemisorption [12], or a combination of
methods. One of these combined procedures is based on
measurement of the H2 consumption during temperature-
programmed-reduction after complete bulk oxidation and
after surface oxidation by N2O adsorption [13,18,20–22].
When Cu-zeolites are concerned, copper sintering can occur
due to heat evolution during the N2O reaction causing
migration and agglomeration of copper externally the zeolite
surface. In this case, temperature-programmed-desorption of
H2 has been successfully adopted [23] to quantitatively
determine metallic surface areas.
As regards the methodology adopted to perform the
analysis, flow as pulse methods have been adopted.
Recently, the technique termed reactive frontal chromato-
graphy (N2O-RFC) [17,24–27] has found a lot of success as
particularly suitable for in situ measurements. This
technique was successfully used for the determination of
copper areas of various catalysts used in the methanol
synthesis. In particular, a nice linear relationship between
the catalytic activity of CuO/ZnO/Al2O3 catalysts and the
total copper surface areas was found [28], indicating the
soundness of the N2O-RFC technique.
A problem accompanying the N2O use is the identifica-
tion of the correct temperature at which only the first copper
surface layer is oxidized without deeper Cu oxidation.
Chinchen et al. [27] have demonstrated that cutting-off the
N2O decomposition at half-monolayer coverage, Cu bulk
oxidation can be avoided. In general, temperatures between
30 and 90 8C are the most frequently used to realize N2O
adsorptive decomposition. However, in this temperature
range, too, occurrence of some deep oxidation of copper
could hinder the obtainment of unambiguous results leading
to overestimation of copper dispersion. Sato et al. [13] have
recently shown that slow bulk oxidation may proceed during
N2O oxidation even at temperature as low as 30 8C. With
increasing N2O exposure time, a linear correlation of Cu
dispersion with t1/2 was found. At temperatures above
100 8C, Cu oxidation by N2O is not restricted to the surface
and bulk oxidation is quite complete [11,19]. On the other
hand, low dispersion values obtained for some supported Cu
catalysts might be due to the presence of ensembles in which
the Cu atoms are not close enough to react with N2O.
Guerreiro et al. [18] suppose that a minimum distance
between surface Cu atoms is required in order to arrive at
N2O adsorptive decomposition, and this might lead to
underestimation of metallic dispersion. The coexistence of
the two opposite effects (overestimation due to deep Cu
oxidation and underestimation due to not correct distance
among Cu atom ensembles) should be ruled out to obtain
reliable results. In spite of all the drawbacks discussed
above, the N2O decomposition is still used to measure the
specific Cu surface area.
In this paper, an easy experimental procedure alternative
to the others already presented in the literature [16,19,20,23]
comprised the reliable N2O-RFC procedure [27], is
proposed. It permits to obtain copper dispersion and specific
copper surface area with qualitative and quantitative
information on the different surface copper species by
combining a surface oxidation by N2O with a successive
analysis of H2 temperature-programmed-reduction of the
freshly oxidized Cu surface (defined as s-TPR, oxidized
surface TPR). s-TPR provides a ‘‘finger-print’’ of the surface
copper species which can be well distinguished from the
bulk ones. The method has been applied to the study of
conventionally prepared CuO-containing catalysts, sup-
ported on silicas of different acidity. Evidence has been
found that the acidity of the support strongly influences the
copper dispersion and copper distribution on the support.
2. Experimental
Copper catalysts were prepared by impregnation of
siliceous supports with aqueous copper acetate solutions to
obtain samples containing about 6 wt.% Cu. The solutions
were gently dropped on the dried powder supports. The
silicas, containing about 13 wt.% of Al2O3 (SA), TiO2 (ST),
and ZrO2 (SZ), were prepared by sol–gel route [29]. All the
powders were dried at 120 8C for 12 h and then calcined at
500 8C for 4 h. The Cu-samples were labelled as Cu/SA, Cu/
ST, and Cu/SZ.
Nitrogen adsorption/desorption isotherms were measured
at 196 8C, using a Sorptometer, type Kelvin 1042, from
Costech International. The adsorbed volume, in
cm3 (STP) g1, was converted into pore volume, cm3 g1,
using the density of N2 in the normal liquid state
(r = 0.8081 g cm3). The molecular area of N2 was taken
to be 16.2 Å2.
Diffraction spectra of the powder samples without any
treatment and after reduction (4.98 vol.% H2/Ar flow at
15 ml min1 at 400 8C for 30 min) were collected using a
Philips PW 1710 apparatus (Cu Ka radiation, 0.154 nm).
The surface analysis was performed by XPS at room
temperature with a M-Probe Surface Science Instrument
spectrophotometer with a monochromatic Al Ka radiation
source operating at 1486.6 eV.
Copper dispersions were calculated from a two-step
analysis consisting of (i) N2O oxidation of Cu to Cu2O and
(ii) H2 temperature-programmed-reduction of the formed
Cu2O surface species (s-TPR). For the analysis, a TPDRO-
1100 (from CE instruments) equipped with a quartz reactor
with a porous septum (i.d., ca. 8 mm) and a filter filled with
soda lime for trapping acidic gases and water was employed.
Samples ground and sieved between 45 and 60 mesh were
used. Before the analysis, in situ pre-reduction of the CuO
phase to Cu(0) was performed at 400 8C (rising the
temperature at a rate of 8 8C min1) in a flowing H2/Ar
mixture for 30 min (4.98 vol.% at 15 ml min1). The first Cu
 A. Gervasini, S. Bennici / Applied Catalysis A: General 281 (2005) 199–205
to Cu2O oxidation by adsorptive decomposition of N2O was
carried out isothermally at different temperatures from 30 to
120 8C by a continuous N2O/He flow for 1 h (0.53 vol.% at
20 cm3 min1). After this, s-TPR was carried out on the
freshly oxidized Cu2O surface in order to reduce Cu2O to
Cu. The reducing gas (4.98 vol.% H2/Ar at flow rate of
15 cm3 min1) entered into the reactor and a thermal
conductivity detector (TCD) measured the amount of H2-
uptake. Heating rates of 20 8C min1 from 40 to 800 8C
were realized. The samples, about 0.15 g, contained 120–
140 mmol of Cu to maintain K- and P-values [30,31] around
150 s and 20 8C, respectively. Quantitative H2-uptakes were
evaluated by integration of the experimental s-TPR curves,
basing on previous calibration measurements with CuO
powder (Fluka, >98 wt.% purity).
Copper dispersion (DCu), defined as the ratio of Cu
exposed at the surface to total Cu, was calculated from the
amount of H2 consumed in the s-TPR analysis. Starting from
the DCu value, Cu metal surface area, MSA, and average
copper particle size, Øav were calculated. Metal surface area
was calculated as: MSA (m2 g1 Cu ) = MolH2 SFNA/
104CMWCu, where MolH2 , SF, NA, CM, and WCu are moles
of hydrogen experimentally consumed per unit mass of
catalyst (mmolH2 g1 cat ), stoichiometric factor (2), Avogadro’s
number (6.022  1023 mol1), number of surface Cu atoms
per unit surface area (1.47  1019 atoms m2), and Cu
content (wt.%), respectively. The O/Cu ratio is assumed to
be 1/2 (SF = 2) on the basis of UPS results [14], which
proved that after oxidation with N2O at temperatures up to
100–120 8C, the surface copper is primarily in the CuI
oxidation state. The CM value of 1.47  1019 atoms m2,
supposing equal areas of exposed (1 0 0), (1 1 0), and (1 1 1)
planes, i.e., 0.065, 0.092, and 0.0563 nm2 [14,18], results in
an average Cu surface area of 0.0711 nm2 per atom. Average
copper particle size was calculated as: Øav
(nm) = 107SKCMWCu/SFMolH2 NArCu, where SK is a
constant depending on Cu particle shape (6 or 5) and rCu is
the density of copper (8.92 g cm3) [18].
Conventional H2 temperature-programmed-reduction
analysis (TPR) was performed under the same experimental
conditions (20 8C min1 from 40 to 800 8C) above reported
on the fully oxidized CuO samples obtained by air treatment
(flow rate of 45 cm3 min1) at 350 8C for 1 h. The ratio
between the s-TPR (obtained after N2O oxidation at 30 8C)
and TPR peak areas directly furnished another evaluation of
Table 1
Bulk and surface characteristics of the dispersed copper catalysts
Code Cu content SA (m2 g1)
(wt.%) (mmol g1
cat )
Cu/SA 5.3 0.834 481
Cu/ST 6.1 0.960 340
Cu/SZ 5.9 0.928 278
a
Determined from H2-uptake extrapolated to ‘‘zero-temperature’’ (see Section 2).
b
Calculated with SK = 6 (spherical or cubic shape of the Cu aggregates).
201
copper dispersion of the studied samples (DCu,A), according
to a method recently reported in the literature [13,18,20].
3. Results and discussion
The main characteristics of the studied samples are
presented in Table 1. The three siliceous supports onto which
copper was deposited by impregnation were high-surface
area materials with large pore volumes [29,32]. The surfaces
possessed variable concentration of acid sites which nature,
and acid strength depended on co-oxide in the silica
structure. As expected, silica–alumina (SA) and silica–
zirconia (SZ) had higher acidity than silica–titania (ST),
both in terms of amount of acid sites and mean acid strength
of their surfaces [29].
The impregnated catalysts had all similar Cu content (ca.
6 wt.%) and high-surface area (300–500 m2 g1). In all the
cases, the calcined catalysts presented a XRD pattern in
which, besides a very broad band at 20–308 2u, typical of
unstructured silica groups, only two definite peaks at 358 and
388 2u appeared. The two peaks are typical of the CuO
presence. On the other hand, the reduced catalysts showed
more definite X-ray peaks at 438 and 508 2u, typical of the
Cu(0) phase. Fig. 1 displays the XRD spectrum of Cu/SZ in
the reduced and unreduced states, as an example. A first
approximate estimate of the CuO particle dimensions was
performed from the broadening of the peak at 358 2u by the
Scherrer law. CuO dimensions of about 15 nm could be
calculated, in any case. The same procedure was applied to
the 438 2u peak of the reduced copper sample, obtaining
dimensions in the 20–30 nm interval for the three samples.
XP spectra revealed surfaces enriched with copper;
signals at binding energy values around 934 eV (Cu 2p3/2)
with very intense and broad satellite peaks at 943 eV were
observed on all the surfaces. From these findings, it can be
deduced that in the fresh catalysts there is the sole Cu(II)
presence [33,34]. Two contributions could be recognized in
the 934 eV convoluted band, the one centered at 933 and the
second at 936 eV. In agreement with similar observations
reported by Córdoba et al. [35] and Bennici et al. [33], the
two signals can be associated to CuO (933 eV) and to Cu–O–
Si–O– (936 eV) species. For the catalyst prepared on the
silica–alumina support (Cu/SA), the presence of Cu(II) ions
in aluminate-like compounds cannot be ruled out. In fact,
D
Cu (%)a MSA* (m2 g1
Cu )
a ?
av (nm)a,b
4.8 30.9 21.8
4.7 30.6 22.0
5.8 37.5 17.9
202 A. Gervasini, S. Bennici / Applied Catalysis A: General 281 (2005) 199–205
Fig. 1. X-ray diffraction patterns of Cu/SZ: (a) fresh (CuO) and (b) reduced
(Cu(0)) samples.
recent results of Shimizu et al. [36] indicate that Cu2+ ions in
CuAl2O4 exhibit an XPS peak around 935 eV.
Central experiments performed on the studied catalysts
were aimed at quantitatively determining the copper surface
dispersion degree. In Table 2 and Fig. 2, we described the
two-step procedure followed for the determination of copper
dispersion. Before the measurements, an appropriate
experimental procedure was applied to the catalysts in
order to reduce the CuO phase to metallic phase (step 0, see
Table 2). The choice of the experimental conditions for step
0 obviously depends on the type of sample; the conditions
have to be optimized in each case. In the present case, the
pre-reducing treatment guaranteed the absence of copper
sintering, at the utmost, a very modest copper aggregation
could occur. In fact, the copper particle size of the reduced
samples, calculated from the relevant XRD spectra, was
similar to that of the calcined CuO samples, above
described.
Step 1 of the combined procedure led to surface oxidation
or to surface and sub-surface oxidation of the Cu particles,
depending on the temperature chosen [11,14,19]. N2O
exposure time also influences the extent of sub-surface
oxidation, all the more so on choosing a higher oxidation
temperature [13]. In the present work, the N2O exposure
time was maintained constant (1 h) and only the temperature
was varied. The consumption of N2O was not directly
Table 2
Stepwise procedure of the combined technique
Step Procedure
0 Pre-reducing treatment with H2/Ar (4.98 vol.%, 15 ml min1)
at 400 8C (8 8C min1) for 30 min, cooling to 40 8C.
Supported copper particles, Cu(0), are formed
1 Isothermal surface oxidation by N2O/He (0.53 vol.%,
20 ml min1) in the 30–120 8C range for 1 h
Surface oxygen besides sub-surface oxygen is taken up
(Cu2O formation)
2 Temperature-programmed-reduction (s-TPR) in H2/Ar
(4.98 vol.%, 15 ml min1) from 40 to 800 8C at 20 8C min1
H2-uptake is determined (Cu2O ! Cu(0) reduction)
Fig. 2. Illustration of the stepwise procedure used.
quantified. As described in Fig. 2, the concentration profile
of N2O, flowing through the powder sample, lowered
following N2O adsorption and then it returned to its initial
value once all the exposed copper sites were oxidized to
Cu2O. The N2O consumed was indirectly evaluated by the
H2-back-titration (step 2 analysis, s-TPR) of the oxygen
atoms left on the surface copper particles (Fig. 2).
The s-TPR profiles (step 2) obtained after N2O oxidation
performed at variable temperatures are reported in Fig. 3b.
The profiles show two well distinct peaks at low (150–
200 8C) and higher temperatures (500–600 8C), over all
three catalysts. The low-temperature peaks did not
remarkably differ in shape and intensity when registered
after N2O oxidation at temperatures in the 30–50 8C interval,
while, for higher oxidation temperatures (up to 120 8C) a
very definite increasing of peak intensity was observed. The
high-temperature peaks were well pronounced only for Cu/
SA, with maxima around 540 8C. The peak areas were not
sensitive to the temperature at which the N2O oxidation was
performed in the overall interval explored (30–120 8C). The
different behaviour of the low- and high-temperature s-TPR
peaks in relation to N2O oxidation temperature suggests that
the low-temperature peak is due to the reduction of Cu2O
species. As higher the oxidation temperature was as more
intense the peak was (higher H2-uptake was observed),
because sub-layer copper oxidation could occur. The high-
temperature peak could be due to the reduction of copper
compounds, probably formed during catalyst preparation
and involving chemical species of the support (e.g.,
CuAl2O4-like compounds). Such Cu-containing compounds
were difficult to be reduced, as indicates the high-
temperature value of the reduction peak. Taking into
account the total amount of copper in the Cu/SA sample,
it can be deduced that about 10% of copper was bound to the
SA support and it was not available as free copper. The mild
conditions used for step 0 were effective for reducing the
CuO phase to Cu(0) but they did not allow reducing the
formed CuAl2O4-like compounds, as emerged from the
reduction profiles of the catalysts collected after pre-
reducing treatment (Fig. 3a). In particular for Cu/SA, a large
and intense peak was still present (at ca. 540 8C) after the
pre-reducing treatment. The area of this peak corresponded
to an H2 consumption of about 90 mmol g1, which is very
 A. Gervasini, S. Bennici / Applied Catalysis A: General 281 (2005) 199–205
Fig. 3. Reduction profiles of Cu/SA (A), Cu/ST (B), and Cu/SZ (C): (a)
TPR after the pre-reducing treatment (step 0 analysis); (b) s-TPR of freshly
oxidized Cu2O phase (step 2 analysis) after N2O oxidation at various
temperatures (step 1 analysis).
similar to that of the high temperature s-TPR peak. Over Cu/
ST and Cu/SZ, the high-temperature peaks are of very low
intensity, indicating very small formation of Cu-containing
compounds during the preparation step. It is hard to know if
the high-temperature peak is associated with exclusive
presence of surface copper phase.
In the light of the evidences emerged from the s-TPR
profiles, we decided to consider only the s-TPR peaks at low
temperatures, related with Cu2O to Cu(0) reduction, in order
to determine the values of copper dispersion (DCu) of all the
samples.
As Fig. 3b shows, increasing Cu2O peak areas were
obtained with the increasing of the temperature of N2O
203
oxidation. Fig. 4 shows the results of H2-back-titration of the
oxygen atoms fixed on the Cu particles by s-TPR. The
obtained curves (H2-uptakes versus N2O oxidation tem-
perature) were S-shaped for the all the three samples. The
hydrogen uptake very slightly increased by increasing the
temperature of oxidation from 30 to 50 8C or to 70 8C for the
Cu/SZ and Cu/SA samples, respectively. Such behaviour
suggests that in this temperature range only the surface
layers of Cu2O are involved in the reduction. Above 50 8C,
for Cu/SZ, or above 70 8C for Cu/SA, there was a sharp
increasing in the hydrogen uptake indicating the reduction of
sub-surface layers. On the other hand, the Cu/ST sample did
not show any constant range of H2-uptake against N2O
oxidation temperature. The peculiar shape of the curves of
Fig. 4, can suggest that the change of slope of the S-shaped
curves indicates the onset of copper bulk oxidation.
The copper dispersion was calculated from the H2-uptakes
determined from the s-TPR analyses, as above described (see
Section 2). For Cu/SA, DCu values around 5% were obtained
following temperatures of Cu oxidation by N2O in the range
32–76 8C; whereas, a value of 17% was calculated following
temperatures of N2O oxidation of 108 8C. Analogously for Cu/
SZ, a quite unique value of DCu (6%) was observed following
temperatures of copper oxidation by N2O in the 29–48 8C
interval, while higher values, 10–12%, were obtained
following oxidation temperatures in the 80–120 8C interval.
For Cu/ST, DCu showed strongly increasing values (from 5 to
14%) in all the temperature range of N2O oxidation
investigated (35–120 8C). Due to the ability of N2O to oxidize
the copper surface and the sub-surface layers depending on the
oxidation temperature chosen, the problem of overestimation
of the copper dispersion arises. To limit this problem,
extrapolation to ‘‘zero-temperature’’ of the curves of Fig. 4,
could allow to obtain true copper dispersion (D
Cu ). The
procedure enables to avoid overestimation of the Cu
dispersion, even if in some cases the Y-intercept of such
curves could be questionable. The D
Cu values with the relevant
specific copper surface areas, MSA*, and average dimensions
of copper aggregates. ?
av , calculated from the hydrogen-
uptakes extrapolated to ‘‘zero-temperature’’ are reported in
Table 1. The D
Cu values, that reflect free copper surfaces, were
in the order Cu/ST  Cu/SA < Cu/SZ. Moreover, the average
copper particle size of the three samples (?
av = 18–22 nm) is
well within the same interval of size obtained from the XRD
analysis (20–30 nm) for the reduced catalysts.
The studied catalysts have copper dispersion similar to
other copper catalysts reported in the literature [13,16,24]
and not important differences emerge among the studied
samples when one considers the free copper phase (Cu/SZ
shows higher value of about 20% than Cu/SA and Cu/ST).
Thus, the preparation method seems to govern the copper
dispersion rather than the support nature. As concerns the
influence of the support nature, the high acidity of SA, which
is due to Al presence, caused an appreciable copper
clustering (about 10%) due to formation of Cu-containing
stable compounds.
204 A. Gervasini, S. Bennici / Applied Catalysis A: General 281 (2005) 199–205

Fig. 4. Influence of the temperature of N2O oxidation reaction (step 1 analysis) on hydrogen-uptake (step 2 analysis) for Cu/SA (A), Cu/ST (B), and Cu/SZ (C).

However, a different picture can be obtained if one
considers the integration of both the low- and high-
temperature peaks of the s-TPR profiles to calculate copper
dispersion of the three catalysts (Fig. 5). The new DCu values
obtained after N2O oxidation at 30 8C of the copper surfaces
and calculated attributing the area of the high-temperature
peak to surface Cu(II) species, are reported in Fig. 5. The
contribution of the high-temperature peak dramatically
influences the copper dispersion value of Cu/SA. A lighter
increasing of Cu dispersion could be calculated for Cu/SZ and
Cu/ST. This is a clear evidence of the influence of the support
nature on the copper aggregation state. Preferential clustering
of copper on alumina rich regions is likely to occur with
interaction between copper and alumina leading to Cu species
more difficult to be reduced than free CuO species.
For comparative purposes and to corroborate the obtained
results, the copper dispersion has been calculated according
to a procedure used in the literature based on the
measurement of the H2 consumption after complete
oxidation of the catalyst and after surface oxidation by
N2O [13,18,20]. By applying this method to the present case,
the ratio between peak areas of conventional TPR profile
(A1), corresponding to total amount of Cu(II) in the sample,
and that of s-TPR (A2) (low-temperature s-TPR peak only),
corresponding to Cu(I) phase formed by N2O oxidation,
directly can give the value of copper dispersion,
DCu,A = 2A2/A1. The values observed for DCu,A and DCu,
when compared after N2O oxidation of the copper phase at
30 8C, are lightly different. DCu,A values (5.8% for Cu/SA,
5.6% for Cu/ST, and 6.8% for Cu/SZ) are all higher than DCu
 A. Gervasini, S. Bennici / Applied Catalysis A: General 281 (2005) 199–205
Fig. 5. Comparison between the H2-uptakes calculated by integration of the
low temperature and the low- and high-temperature s-TPR peaks after N2O
oxidation at 30 8C. The relevant percent copper dispersion values are
indicated.
(4.8% for Cu/SA, 5.3% for Cu/ST, and 5.8% for Cu/SZ).
Non-quantitative reduction of CuO to Cu(0) during
conventional TPR analysis can be responsible of this
behaviour, leading to underestimation of the A1 peak areas.
4. Conclusion
Oxidized surface layers of copper phase (Cu2O) was
reduced (s-TPR) allowing the measurement of specific Cu
surface area and identification of different surface copper
species. The used method was applied to catalysts prepared
by conventional impregnation, which is still a convention-
ally adopted preparation in chemical industry. The method
consists in an isothermal surface oxidation by N2O at
definite temperature followed by H2-back-titration (s-TPR),
it can be suitable for routine measurements of copper
dispersion. Homogeneous series of copper catalysts may be
comparatively studied by performing the N2O surface
oxidation in low-temperature range (30–50 8C), and then
counting the oxygen left at the surface. Due to the high
sensitivity of the two-step technique, catalysts at low Cu
loading, as those used for environmental purposes, could be
studied.
Moreover, the qualitative and quantitative determination
of different surface copper species can be performed by s-
TPR analysis. Knowledge of the type and amount of the
surface copper species may be of some interest for the
calculation of the turnover-frequency values when inter-
pretation of catalytic performances for reactions catalysed
by copper phases is desired.
Acknowledgements
The authors wish to thank Ms. Iolanda Biraghi for
performing XRD measurements and Professor Vittorio
205
Ragaini for helpful suggestions during the course of this
work.
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