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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 (DCu ) 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.
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 In this paper, an easy experimental procedure alternative
freezing out the excess of N2O [9,11], chromatographic to the others already presented in the literature [16,19,20,23]
separation of unreacted N2O and N2 formed [8,14], comprised the reliable N2O-RFC procedure [27], is
gravimetric determination of the increasing in weight of the proposed. It permits to obtain copper dispersion and specific
sample due to oxygen chemisorption [12], or a combination of copper surface area with qualitative and quantitative
methods. One of these combined procedures is based on information on the different surface copper species by
measurement of the H2 consumption during temperature- combining a surface oxidation by N2O with a successive
programmed-reduction after complete bulk oxidation and analysis of H2 temperature-programmed-reduction of the
after surface oxidation by N2O adsorption [13,18,20–22]. freshly oxidized Cu surface (defined as s-TPR, oxidized
When Cu-zeolites are concerned, copper sintering can occur surface TPR). s-TPR provides a ‘‘finger-print’’ of the surface
due to heat evolution during the N2O reaction causing copper species which can be well distinguished from the
migration and agglomeration of copper externally the zeolite bulk ones. The method has been applied to the study of
surface. In this case, temperature-programmed-desorption of conventionally prepared CuO-containing catalysts, sup-
H2 has been successfully adopted [23] to quantitatively ported on silicas of different acidity. Evidence has been
determine metallic surface areas. found that the acidity of the support strongly influences the
As regards the methodology adopted to perform the copper dispersion and copper distribution on the support.
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 2. Experimental
particularly suitable for in situ measurements. This
technique was successfully used for the determination of Copper catalysts were prepared by impregnation of
copper areas of various catalysts used in the methanol siliceous supports with aqueous copper acetate solutions to
synthesis. In particular, a nice linear relationship between obtain samples containing about 6 wt.% Cu. The solutions
the catalytic activity of CuO/ZnO/Al2O3 catalysts and the were gently dropped on the dried powder supports. The
total copper surface areas was found [28], indicating the silicas, containing about 13 wt.% of Al2O3 (SA), TiO2 (ST),
soundness of the N2O-RFC technique. and ZrO2 (SZ), were prepared by sol–gel route [29]. All the
A problem accompanying the N2O use is the identifica- powders were dried at 120 8C for 12 h and then calcined at
tion of the correct temperature at which only the first copper 500 8C for 4 h. The Cu-samples were labelled as Cu/SA, Cu/
surface layer is oxidized without deeper Cu oxidation. ST, and Cu/SZ.
Chinchen et al. [27] have demonstrated that cutting-off the Nitrogen adsorption/desorption isotherms were measured
N2O decomposition at half-monolayer coverage, Cu bulk at 196 8C, using a Sorptometer, type Kelvin 1042, from
oxidation can be avoided. In general, temperatures between Costech International. The adsorbed volume, in
30 and 90 8C are the most frequently used to realize N2O cm3 (STP) g1, was converted into pore volume, cm3 g1,
adsorptive decomposition. However, in this temperature using the density of N2 in the normal liquid state
range, too, occurrence of some deep oxidation of copper (r = 0.8081 g cm3). The molecular area of N2 was taken
could hinder the obtainment of unambiguous results leading to be 16.2 Å2.
to overestimation of copper dispersion. Sato et al. [13] have Diffraction spectra of the powder samples without any
recently shown that slow bulk oxidation may proceed during treatment and after reduction (4.98 vol.% H2/Ar flow at
N2O oxidation even at temperature as low as 30 8C. With 15 ml min1 at 400 8C for 30 min) were collected using a
increasing N2O exposure time, a linear correlation of Cu Philips PW 1710 apparatus (Cu Ka radiation, 0.154 nm).
dispersion with t1/2 was found. At temperatures above The surface analysis was performed by XPS at room
100 8C, Cu oxidation by N2O is not restricted to the surface temperature with a M-Probe Surface Science Instrument
and bulk oxidation is quite complete [11,19]. On the other spectrophotometer with a monochromatic Al Ka radiation
hand, low dispersion values obtained for some supported Cu source operating at 1486.6 eV.
catalysts might be due to the presence of ensembles in which Copper dispersions were calculated from a two-step
the Cu atoms are not close enough to react with N2O. analysis consisting of (i) N2O oxidation of Cu to Cu2O and
Guerreiro et al. [18] suppose that a minimum distance (ii) H2 temperature-programmed-reduction of the formed
between surface Cu atoms is required in order to arrive at Cu2O surface species (s-TPR). For the analysis, a TPDRO-
N2O adsorptive decomposition, and this might lead to 1100 (from CE instruments) equipped with a quartz reactor
underestimation of metallic dispersion. The coexistence of with a porous septum (i.d., ca. 8 mm) and a filter filled with
the two opposite effects (overestimation due to deep Cu soda lime for trapping acidic gases and water was employed.
oxidation and underestimation due to not correct distance Samples ground and sieved between 45 and 60 mesh were
among Cu atom ensembles) should be ruled out to obtain used. Before the analysis, in situ pre-reduction of the CuO
reliable results. In spite of all the drawbacks discussed phase to Cu(0) was performed at 400 8C (rising the
above, the N2O decomposition is still used to measure the temperature at a rate of 8 8C min1) in a flowing H2/Ar
specific Cu surface area. mixture for 30 min (4.98 vol.% at 15 ml min1). The first Cu
A. Gervasini, S. Bennici / Applied Catalysis A: General 281 (2005) 199–205 201
to Cu2O oxidation by adsorptive decomposition of N2O was copper dispersion of the studied samples (DCu,A), according
carried out isothermally at different temperatures from 30 to to a method recently reported in the literature [13,18,20].
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 3. Results and discussion
Cu. The reducing gas (4.98 vol.% H2/Ar at flow rate of
15 cm3 min1) entered into the reactor and a thermal The main characteristics of the studied samples are
conductivity detector (TCD) measured the amount of H2- presented in Table 1. The three siliceous supports onto which
uptake. Heating rates of 20 8C min1 from 40 to 800 8C copper was deposited by impregnation were high-surface
were realized. The samples, about 0.15 g, contained 120– area materials with large pore volumes [29,32]. The surfaces
140 mmol of Cu to maintain K- and P-values [30,31] around possessed variable concentration of acid sites which nature,
150 s and 20 8C, respectively. Quantitative H2-uptakes were and acid strength depended on co-oxide in the silica
evaluated by integration of the experimental s-TPR curves, structure. As expected, silica–alumina (SA) and silica–
basing on previous calibration measurements with CuO zirconia (SZ) had higher acidity than silica–titania (ST),
powder (Fluka, >98 wt.% purity). both in terms of amount of acid sites and mean acid strength
Copper dispersion (DCu), defined as the ratio of Cu of their surfaces [29].
exposed at the surface to total Cu, was calculated from the The impregnated catalysts had all similar Cu content (ca.
amount of H2 consumed in the s-TPR analysis. Starting from 6 wt.%) and high-surface area (300–500 m2 g1). In all the
the DCu value, Cu metal surface area, MSA, and average cases, the calcined catalysts presented a XRD pattern in
copper particle size, Øav were calculated. Metal surface area which, besides a very broad band at 20–308 2u, typical of
was calculated as: MSA (m2 g1 Cu ) = MolH2 SFNA/ unstructured silica groups, only two definite peaks at 358 and
104CMWCu, where MolH2 , SF, NA, CM, and WCu are moles 388 2u appeared. The two peaks are typical of the CuO
of hydrogen experimentally consumed per unit mass of presence. On the other hand, the reduced catalysts showed
catalyst (mmolH2 g1 cat ), stoichiometric factor (2), Avogadro’s more definite X-ray peaks at 438 and 508 2u, typical of the
number (6.022 1023 mol1), number of surface Cu atoms Cu(0) phase. Fig. 1 displays the XRD spectrum of Cu/SZ in
per unit surface area (1.47 1019 atoms m2), and Cu the reduced and unreduced states, as an example. A first
content (wt.%), respectively. The O/Cu ratio is assumed to approximate estimate of the CuO particle dimensions was
be 1/2 (SF = 2) on the basis of UPS results [14], which performed from the broadening of the peak at 358 2u by the
proved that after oxidation with N2O at temperatures up to Scherrer law. CuO dimensions of about 15 nm could be
100–120 8C, the surface copper is primarily in the CuI calculated, in any case. The same procedure was applied to
oxidation state. The CM value of 1.47 1019 atoms m2, the 438 2u peak of the reduced copper sample, obtaining
supposing equal areas of exposed (1 0 0), (1 1 0), and (1 1 1) dimensions in the 20–30 nm interval for the three samples.
planes, i.e., 0.065, 0.092, and 0.0563 nm2 [14,18], results in XP spectra revealed surfaces enriched with copper;
an average Cu surface area of 0.0711 nm2 per atom. Average signals at binding energy values around 934 eV (Cu 2p3/2)
copper particle size was calculated as: Øav with very intense and broad satellite peaks at 943 eV were
(nm) = 107SKCMWCu/SFMolH2 NArCu, where SK is a observed on all the surfaces. From these findings, it can be
constant depending on Cu particle shape (6 or 5) and rCu is deduced that in the fresh catalysts there is the sole Cu(II)
the density of copper (8.92 g cm3) [18]. presence [33,34]. Two contributions could be recognized in
Conventional H2 temperature-programmed-reduction the 934 eV convoluted band, the one centered at 933 and the
analysis (TPR) was performed under the same experimental second at 936 eV. In agreement with similar observations
conditions (20 8C min1 from 40 to 800 8C) above reported reported by Córdoba et al. [35] and Bennici et al. [33], the
on the fully oxidized CuO samples obtained by air treatment two signals can be associated to CuO (933 eV) and to Cu–O–
(flow rate of 45 cm3 min1) at 350 8C for 1 h. The ratio Si–O– (936 eV) species. For the catalyst prepared on the
between the s-TPR (obtained after N2O oxidation at 30 8C) silica–alumina support (Cu/SA), the presence of Cu(II) ions
and TPR peak areas directly furnished another evaluation of in aluminate-like compounds cannot be ruled out. In fact,
Table 1
Bulk and surface characteristics of the dispersed copper catalysts
Code Cu content SA (m2 g1) DCu (%)a MSA* (m2 g1
Cu )
a ? av (nm)a,b
(wt.%) (mmol g1
cat )
Cu/SA 5.3 0.834 481 4.8 30.9 21.8
Cu/ST 6.1 0.960 340 4.7 30.6 22.0
Cu/SZ 5.9 0.928 278 5.8 37.5 17.9
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).
202 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 For comparative purposes and to corroborate the obtained
considers the integration of both the low- and high- results, the copper dispersion has been calculated according
temperature peaks of the s-TPR profiles to calculate copper to a procedure used in the literature based on the
dispersion of the three catalysts (Fig. 5). The new DCu values measurement of the H2 consumption after complete
obtained after N2O oxidation at 30 8C of the copper surfaces oxidation of the catalyst and after surface oxidation by
and calculated attributing the area of the high-temperature N2O [13,18,20]. By applying this method to the present case,
peak to surface Cu(II) species, are reported in Fig. 5. The the ratio between peak areas of conventional TPR profile
contribution of the high-temperature peak dramatically (A1), corresponding to total amount of Cu(II) in the sample,
influences the copper dispersion value of Cu/SA. A lighter and that of s-TPR (A2) (low-temperature s-TPR peak only),
increasing of Cu dispersion could be calculated for Cu/SZ and corresponding to Cu(I) phase formed by N2O oxidation,
Cu/ST. This is a clear evidence of the influence of the support directly can give the value of copper dispersion,
nature on the copper aggregation state. Preferential clustering DCu,A = 2A2/A1. The values observed for DCu,A and DCu,
of copper on alumina rich regions is likely to occur with when compared after N2O oxidation of the copper phase at
interaction between copper and alumina leading to Cu species 30 8C, are lightly different. DCu,A values (5.8% for Cu/SA,
more difficult to be reduced than free CuO species. 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) 199–205 205
References