Applied Catalysis A: General 239 (2003) 8794

Surface structure and catalytic behavior of silica-supported copper catalysts prepared by impregnation and solgel methods
Zhenl Wang, Qingsheng Liu, Jianfeng Yu, Tonghao Wu, Guojia Wang
Department of Chemistry, Jilin University, Changchun 130023, PR China Received 6 February 2002; received in revised form 24 June 2002; accepted 24 June 2002

Abstract Supported copper on silica catalysts prepared by solgel and impregnation methods were studied in this paper. The surface structures of these catalysts were characterized by various techniques, including BET, XRD, FTIR, XPS, TPR, and ESR. The results showed that the distribution of copper species was in different ways in the catalysts prepared by the two methods. Cu(II) species highly dispersed in the silica matrix for the solgel catalyst, while copper oxide clusters are dominant in the CuO-SiO2 sample prepared by the impregnation method. The catalysts were then used for dehydrogenation of 2-butanol. Obvious differences of catalytic behavior were observed for the catalysts prepared by the two methods. High selectivity (>90%) toward dehydrogenation and high 2-butanol conversion was observed for the impregnated catalyst; however, for the CuO-SiO2 solgel catalyst, very low dehydrogenation selectivity and 2-butanol conversion were obtained. The surface structures of catalysts were closely related to the preparation methods, and the catalytic behaviors were affected subsequently. The copper oxide clusters, which may be reduced to Cu0 , are responsible for the dehydrogenation reaction. The highly dispersed Cu(II) ions were inactive for catalyze 2-butanol dehydrogenation. 2002 Elsevier Science B.V. All rights reserved.
Keywords: Cu-SiO2 ; Solgel; Impregnation; 2-Butanol; Dehydrogenation

1. Introduction Supported copper catalysts have been attracted considerable attention due to recent practical uses in promoting methanol steam reforming [1], dehydrogenation [2], and ester hydrogenolysis [3]. It is important to study the preparation method and the nature of the interaction between the support material and the catalytic species in gaining a deeper understanding of copper-containing catalysts. To achieve high catalytic activity, it is necessary to disperse ne particles in well-dened pores
Corresponding author. Tel.: +86-431-8922331x3214; fax: +86-431-8949334. E-mail address: wguojia@mail.jlu.edu.cn (G. Wang).

in a support. By conventional methods for catalyst preparation such as impregnation, however, inhomogeneous agglomeration of active species at grain boundary of support occurs especially at higher content, and large-sized particles result [4]. Although the ion-exchange method stabilizes copper species on silica and leads to the better dispersion of copper on silica than the wet impregnation method does [5], this ion-exchange method can not be widely used because of the low loading due to the limit terminal OH groups on the surface of silica. For stabilizing of the active phase in supported copper catalyst, the solgel technique offers some advantages. With this preparation method, copper species are effectively incorporated into ionic oxide network [6,7] and the method may led to more stable catalysts than those

0926-860X/02/$ see front matter 2002 Elsevier Science B.V. All rights reserved. PII: S 0 9 2 6 - 8 6 0 X ( 0 2 ) 0 0 4 2 1 - 0

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prepared by conventional methods. Because synthesis parameters are available, solgel processing offers versatility in nal material properties not available by other catalyst synthesis methods [810]. However, lower activities were usually observed due to encapsulation in some solgel catalysts [11]. It has been suggested that more than one form of copper species exist on the surface of catalysts. Depending on the different preparation processes and experimental conditions, various species would play different roles in catalytic reactions [1215]. Guerreiro et al. [14] reported the presence of low-interacted Cu(II) species, highly dispersed and surface-interacted species in silica-supported copper catalyst prepared by ionic exchange. Sakata et al. [16] reported that isolated and aggregated copper(II) ions co-existed on the Cu-Pd-H3 PO4 /SiO2 catalyst. The isolated Cu(II) ions coordination with PO4 3 was found to be reversible with alternate reductionoxidation treatments and was responsible for catalytically active sites in the direct oxidation of benzene. Marchi et al. [17] reported that two CuO phases are present on the CuO-SiO2 catalyst with different properties. In the present work, silica-supported copper catalysts were prepared by solgel technique and conventional impregnation method, and the two types were calcined at the same temperature. The surface structures of the catalysts were studied by BET, XPS, XRD, FTIR, and ESR techniques. The 2-butanol-dehydrogenation was chosen as a testing reaction to investigate the catalytic behaviors of the catalysts. The main aim is to understand the relationships among the preparation methods, the surface structure and the catalytic performances of these catalysts. 2. Experimental 2.1. Catalyst preparation The CuO-SiO2 samples were prepared by the solgel techniques from Si(OC2 H5 )4 (TEOS) and Cu(NO3 )2 3H2 O precursors with CuO content of 5.0 wt.%. This method has been successfully used for preparing Me-SiO2 (Me = ZnO, Fe2 O2 ) nanocomposites [18,19]. TEOS was mixed with ethanol and an aqueous solution of Cu(NO3 )3H2 O. The molar ratio TEOS:C2 H5 OH:H2 O was 1:3.85:10.2. After 1 h

stirring, the clear sol was then poured into a Teon beaker and allowed to gel in air. The gel was dried in an oven by slowly raising the temperature to 100 C over a week. The sample was then powdered and heated to 500 C, in steps of 100 C maintaining the temperature at each step for 30 min. Such a sample was denoted as SG. The CuO-SiO2 catalyst containing 5 wt.% of CuO was synthesized by the incipient-wetness impregnation method. The SiO2 was impregnated with an aqueous solution of Cu(NO3 )2 3H2 O. The slurry formed was dried at 70 C for 18 h, and then calcined in the same process as used for SG catalyst. The prepared sample is denoted as IM. 2.2. Catalyst characterization BET specic surface areas of the samples were measured on a Micromeritics ASAP 2010 system under liquid-N2 temperature using N2 as the adsorbate. The XRD analyses were recorded on a D/Max-rA diffractometer. The scans were taken in a 2 = 2080 range with step size of 0.05 using Cu K radiation at 50 kV and 150 mA. The chemical states of the copper particles were checked by a VG ESCA LAB MK II XPS system, using a standard Al K (1486.6 eV) source. Charging effects were corrected by adjusting the C 1s peak to 284.6 eV. ESR measurements were made at room temperature on a Bruker ER 200D-SRC spectrometer operated at X-Band frequencies, 9.8 GHz Klystron frequencies, and 100 KHz magnetic eld modulations. DPPH was used as a eld marker (g = 2.0036). FTIR measurements were performed on a Nicolet-impact 410 spectrometer (KBr tablet). Spectra were recorded in the range of 4000400 cm1 . Temperature programmed reduction (TPR) was carried out in a ow reactor system. Fifty milligram catalyst was placed in a quartz reactor, the reduction gas was 5% H2 Ar mixture with a total ow rate of 30 cm3 /min. The heating rate was 10 C/min with the range 100800 C and using a thermal conductivity detector measured the hydrogen consumption. The mixture was dried in a molecular-sieves trap. 2.3. Catalyst testing The catalytic conversion of 2-butanol was carried out in a xed bed microreactor operated at atmospheric

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pressure. The typical run was performed on 0.3 g of catalyst sieved to 4060 mesh and pretreated in situ for 0.5 h by a ow of pure argon at 673 K. 2-Butanol was directly introduced into the reactor with a pulseless pump (made in Beijing, China) without any carrier gas. The GHSV was maintained at 1600 h1 at the reaction temperature. The reaction mixture was analyzed quantitatively by on-line gas chromatography equipped with a ame detector and an integrator (Shimadzu C-R6A Chromatopac).

Table 1 BET surface characterization of SG and IM catalysts Catalysts SG IM SiO2 BET surface areas (m2 /g) 425.1 365.4 435.2 Average pore diameters () 21.8 21.2 24.8 Colors Clear blue Dark gray White

3. Results and discussion 3.1. Surface properties BET surface data of SG and IM catalysts are summarized in Table 1, together with the colors of the fresh catalysts. The specic surface area of SG catalyst (425.1 m2 /g) is higher than that of IM catalyst (365.4 cm2 /g), suggesting that higher specic surface areas can be obtained by the solgel method. The IM samples show a clear decrease in specic surface areas and average pore diameters relative to their supports. This is expected because the pores in each support are partially lled by CuO particles. The IM sample is dark

gray in color, which suggests that CuO phase exists in the sample. However, the SG catalyst is clear blue, characteristic of the presence of cupric ions Cu2+ incorporated into silica [20], indicating that Cu cations are dispersed in silica gel matrix in atomic level and that no separate CuO phase was formed during the calcination [4]. Fig. 1 shows the XRD patterns of both calcinated (fresh) and reduced (used) SG and IM catalysts. The SG catalysts, both fresh and used, do not show the signal of either metallic copper or of copper oxide but do show a broad peak attributed to amorphous silica (Fig. 1a and b), This indicates that the copper species particles, which are amorphous or very small, are highly dispersed within the matrix. In the case of IM catalysts, the typical pattern of CuO is observed in the fresh catalyst (Fig. 1c) and three peaks, centered at 43.4, 50.3, and 74.1 , attributed to metal

Fig. 1. X-ray diffraction patterns of (a) fresh SG catalyst; (b) used SG catalyst; (c) fresh IM catalyst and (d) used IM catalyst.

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Fig. 2. FTIR spectra of (a) SG catalyst and (b) IM catalyst.

copper crystallite appear in the used one (Fig. 1d). The results indicate that Cu species would be better stabilized in the silica support by this solgel method than by impregnation method during the calcination. The typical FTIR absorbance spectra of SG and IM catalysts are shown in Fig. 2. No obvious difference is observed between SG and IM catalysts. The spectra have a broad absorption band at approximately 3460 cm1 , which is assigned to the OH stretching vibration of water, ethanol and silanols. Similarly, the band near 1630 cm1 is associated with the bending mode of OH groups of adsorbed water [21]. Bands at approximately 1200 and 1100 cm1 correspond to stretching vibrations of SiO bonds; that at 964.2 cm1 is due to the presence of non-bonded oxygen SiO [22]. The bands at approximately 800 and 575 cm1 are also attributed to bending vibrations of SiO bonds, and that at 464.7 cm1 belongs to bending vibrations of OSiO bonds [23]. The vibration of CuO bonds that appear at 575, 500, and 460 cm1 [24] cannot be observed due to the presence of a broad band at 467.4 cm1 from the silica support. In order to obtain more information about the Cu species in the samples, the chemical compositions of the catalysts were determined by X-ray photoelectron spectroscopy (Figs. 3 and 4). For SG catalysts, the Cu 2p3/2 peak is at 933.7 eV with a shoulder on the

high BE side, which is characteristic of Cu2+ species [25,26] in a fresh sample (Fig. 3a), and the intensity of the satellites shows no obvious decrease after the reaction (Fig. 3b). The color of the sample is still clear blue. The results suggest that the Cu(II) species does not change during the reaction. In the case of fresh IM catalyst, the position of the Cu 2p3/2 peak

Fig. 3. The XPS spectra of Cu 2p3/2 core level of (a) fresh SG catalyst; (b) used SG catalyst; (c) fresh IM catalyst and (d) used IM catalyst.

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Fig. 4. The XPS spectra of Cu LLM lines of (a) fresh IM catalyst and (b) used IM catalyst.

is at 934.2 eV (Fig. 3c) and the Cu LMM peak is at 569.4 eV (Fig. 4a), consistent with CuO [27,28]. The Cu2+ satellites are clearly visible in the Cu 2p XPS spectrum. After reaction, the Cu2+ satellites nearly disappeared, the Cu 2p3/2 peak shifted to 932.5 eV (Fig. 3d), and the Cu LMM shifted to 568.2 eV (Fig. 4b), consistent with the formation of copper metal [27,28].

Electron spin resonance (ESR) is an absolutely necessary method to investigate the Cu(II) species in the catalysts. The room temperature ESR spectra of SG and IM catalysts are reported in Fig. 5. A strong axially symmetric signal (g = 2.07) is obtained for fresh SG catalyst (Fig. 5a). The axially symmetrical signals, which are generally attributed to highly dispersed or isolated Cu(II) species interacting with the support, have been reported in the ESR studies [15,2931]. Lack of hyperne structure may be due to clusters located on the support. The ESR spectrum of the used SG catalyst is shown in Fig. 5b. The ESR signal is narrower than that of the fresh catalyst and exhibits a typical hyperne axially symmetrical structure. The parameters (gxx = gyy = g = 2.07 and gzz = g = 2.36, A = 140 G) are close to the ones reported for highly dispersed Cu(II) coordinated with lattice oxygen of the support [3234]. The phenomena suggest that highly dispersed Cu(II) species prevail in the SG catalyst and that clusters are also present. After reaction, the clusters disappear and the highly dispersed Cu(II) species are still present. For IM catalysts, the ESR result showed a difference case compared with that of SG sample. Fig. 5c shows that the axial symmetric becomes broader and its intensity decreases with respect to SG catalyst. The broad isotropic signal can probably be attributed to

Fig. 5. ESR proles of (a) fresh SG catalyst; (b) used SG catalyst and (c) IM catalyst.

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dipolar and spinspin exchange interactions among Cu(II) ions of clusters, which are located close to one another. The result indicates that copper oxide clusters are the main form in the IM catalyst. Temperature-programmed reduction, containing some information about the surface structure of the catalysts, has been extensively applied to the characterization of reducible catalysts including metal and metal oxide system. It is especially suitable for studying highly dispersed systems with low loading. The species of copper in the catalysts are strongly affected by the support, loading, preparation methods, calcination temperature, and experimental conditions. Depending on different factors, the TPR shows one, two, or three peaks in a wide temperature range (230800 C). Dow et al. [35] investigated the TPR of supported CuO in hydrogen. For copper oxide supported on -Al2 O3 , two TPR peaks can be observed. The peak at low temperature region is attributed to the reduction of a highly dispersed copper species and the peak at high temperature region is ascribed to the reduction of bulk CuO. The highly dispersed copper species include isolated Cu2+ ions that strongly interact with the support and the isolated Cu2+ that weakly interact with the support (the cupric ions have close contact

with each other), and small two-dimensional clusters or three-dimensional ones. The peak at higher temperature is attributed to large three-dimensional clusters. Here, three TPR peaks are observed in IM catalyst (Fig. 6b). The peak centered at 356 C would be ascribed to the reduction of larger CuO clusters. The two lower reduced centered at 287 and 245 C, should be due to the reduction of highly dispersed Cu(II) species and small CuO clusters, respectively. From the intensities of peaks, it can be conrmed that the main copper species present on the IM catalyst are larger CuO clusters. For SG catalyst, only two peaks in the low temperature region are observed (Fig. 6a) compared to IM catalyst in the TPR prole. The results suggest that no larger CuO particles but only highly dispersed Cu(II) species and small clusters exist in SG catalyst, which is in agreement with XRD results. 3.2. Catalytic activity The 2-butanol dehydrogenation has been widely used for correlating selectivity with physicochemical properties of the catalysts. In the present paper, the catalytic activities for 2-butanol dehydrogenation on SG and IM catalysts as a function of reaction temperature are shown in Table 2.

Fig. 6. TPR spectra of (a) SG catalyst and (b) IM catalyst.

Z. Wang et al. / Applied Catalysis A: General 239 (2003) 8794 Table 2 Catalytic activities for 2-butanol dehydrogenation on SG and IM catalysts Catalysts Reaction temperature ( C) 230 290 350 220 280 350 Selectivity (%) MEK 15.6 15.7 99.8 97.8 92.1 Butene 84.4 84.3 0.2 1.9 6.2 Conversion of 2-butanol (%) 0 1.5 4.1 67.4 93.4 99.0

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SG

IM

Reaction conditions: reaction time is 20 min; GHSV = 1600 h1 , no carrier gas; catalysts: 0.30 g. Before reaction each catalyst is pretreated by argon for 30 min at 400 C. MEK = methyl-ethylketone.

One may observe from the table that the high selectivity to methyl-ethyl-ketone (MEK, the dehydrogenation product) is obtained at all the reaction temperatures for IM catalyst. The selectivity decreases from 99.8 to 92.1% and the 2-butanol conversion increases from 67.4 to 99.0% with reaction temperature increase. For SG sample, very low conversion of 2-butanol is observed. Only 4.1% 2-butanol converted to products even if the reaction temperature increased up to 350 C. At the same time, relatively low selectivity to MEK is observed (about 16%) over all the range of reaction temperature. From the above characterization of catalysts, we conclude that the differences of selectivity and conversion would not be related to the SBET (both SG and IM have the similar surface data). The state and distribution of Cu species in the catalysts are the key factors to the reaction. Several relevant investigations have dealt with the importance of the different oxidation states of copper in the dehydrogenation reactions. However, there is not yet a general agreement between the authors. Most of the studies suggest dehydrogenation mechanisms involving both Cu2+ , Cu+ , and Cu0 species [17,3638]. Marchi et al. [17] reported that the CuO phase with a low reduction temperature, a small particle size and a poor crystallinity is the one responsible for the appearance of the nely dispersed Cu0 , which is the active phase for 2-propanol dehydrogenation on a Cu-SiO2 catalyst. In this paper, no Cu+ species is detected in the fresh or used SG and IM catalysts. For SG catalysts, the

main form of Cu species is highly dispersed Cu(II) ions, and it is stable during the reaction. The small amount of clusters detected in fresh SG catalyst, however, disappears after reaction. Low selectivity to dehydrogenation and 2-butanol conversion are observed on this catalyst. For IM catalyst, the main form is CuO cluster, including small or larger clusters, which are reduced to Cu0 during the reaction (Fig. 1). At the same time, high selectivity to dehydrogenation and 2-butanol conversion are obtained. So it is easy to conclude that the ability of dehydrogenation is related to the CuO clusters, which may be reduced to Cu0 during dehydrogenation reaction, and Cu0 is the main reactive site for dehydrogenation of 2-butanol. The results suggest that the highly dispersed Cu(II) ions were not the active phase for dehydrogenation. This phenomenon is probably attributed to isolated Cu(II) enveloped within the SiO2 matrix or strongly interacting with the support, which might nd access difcult or reduced by 2-butanol molecules. This viewpoint is in agreement with that of Guerreiro et al. [14], who reported that highly dispersed copper (isolated Cu species) is unable to catalyze the dehydrogenation of methanol.

4. Conclusion High selectivity to dehydrogenation and high conversion of 2-butanol were observed on IM catalyst and low selectivity to MEK and low 2-butanol conversion were observed on the SG sample. Based on the results of XRD, XPS, ESR, and TPR, the different distribution of cupric species over SG and IM catalyst have been observed: highly dispersed Cu(II) species are the main form in the former but clusters are predominant in the latter. The surface structure of the catalysts is determined by the preparation method. The activities of dehydrogenation of the SG and IM catalysts were strongly dependent on their surface structures. The CuO clusters that may be reduced to metallic copper are responsible for the dehydrogenation reaction. But the highly dispersed copper(II) species that cannot be reduced were inactive to catalyze the dehydrogenation reaction. The results presented here provided insight into how the surface structures of catalysts were determined by the preparation methods and how the catalytic behaviors were consequently affected.

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