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international journal of hydrogen energy 33 (2008) 4569–4576 Available at www.sciencedirect.com journal homepage: www.elsevier.com/locate/he Synthesis and characterization of bimetallic Cu–Ni/ZrO2 nanocatalysts: H2 production by oxidative steam reforming of methanol ´rez-Hernandeza,*, G. Mondrago Galiciaa, D. Mendoza Anayaa, J. Palaciosa, ´ ´n R. Pe b C. Angeles-Chavez , J. Arenas-Alatorrec ´xico-Toluca S/N La Marquesa, Ocoyoacac, Instituto Nacional de Investigaciones Nucleares; Carretera Me ´xico C.P. 52750, Mexico Estado de Me b ´leo, Eje Central La ´zaro Ca ´rdenas, Programa de Ingenierıa Molecular, Instituto Mexicano del Petro ´ ´xico D.F., Mexico No. 152, C.P. 07730, Me c ´xico D.F., Mexico Instituto de Fısica-UNAM, Apartado Postal 20-364, C.P. 01000, Me ´ a article info Article history: Received 19 May 2008 Received in revised form 11 June 2008 Accepted 13 June 2008 Available online 22 August 2008 Keywords: Cu–Ni/ZrO2 catalysts Bimetallic nanocatalysts H2 production Oxidative steam reforming of methanol HRTEM STEM–EDX TPR abstract Cu/ZrO2, Ni/ZrO2 and bimetallic Cu–Ni/ZrO2 catalysts were prepared by deposition– precipitation method to produce hydrogen by oxidative steam reforming of methanol (OSRM) reaction in the range of 250–360  C. TPR analysis of the Cu–Ni/ZrO2 catalyst showed that the presence of Cu facilitates the reduction of the Ni at lower temperatures. In addition, this sample showed two reduction peaks, the former peak was attributed to the reduction of the adjacent Cu and Ni atoms which could be forming a bimetallic Cu-rich phase, and the second was assigned to the remaining Ni atoms forming bimetallic Nirich nanoparticles. Transmission Electron Microscopy revealed Cu or Ni nanoparticles on the monometallic samples, while bimetallic nanoparticles were identified on the Cu–Ni/ ZrO2 catalyst. On the other hand, Cu–Ni/ZrO2 catalyst exhibited better catalytic activity than the monometallic samples. The difference between them was related to the Cu–Ni nanoparticles present on the former catalyst, as well as the bifunctional role of the bimetallic phase and the support that improve the catalytic activity. All the catalysts showed the same selectivity toward H2 at the maximum reaction temperature and it was w60%. The high selectivity toward CO is associated to the presence of the bimetallic Ni-rich nanoparticles, as evidenced by TEM–EDX analysis, since this behavior is similar to the one showed by the monometallic Ni-catalyst. ª 2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved. 1. Introduction The PEM (proton-exchange membrane) fuel cell generally requires H2 as fuel; there are various strategies for on board storage of H2 in the vehicle: gas compressed, liquid, H2 storage materials such as metal hydrides and carbon nanotubes. However, all these options require a dedicated filling station infrastructure which raises issues concerning safety and * Corresponding author. Tel.: þ52 55 53297239; fax: þ52 55 53297240. ´ ´ E-mail address: raul.perez@inin.gob.mx (R. Perez-Hernandez). 0360-3199/$ – see front matter ª 2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.ijhydene.2008.06.019 4570 international journal of hydrogen energy 33 (2008) 4569–4576 cost. Olah [1] put forth a convincing case for why the chemical storage of hydrogen in the form of methanol offers distinct advantages over alternate means. The main advantage of liquid fuels is their high energy density and ease of handling, and the fact that they can be used for the on-demand production of hydrogen for fuel cells, with applications in mobile and stationary grid-independent power systems. Methanol is readily available and can be catalytically reformed into an H2-rich gas at moderated temperature (200–400  C). Methanol has high H/C ratio and no C–C bonds, hence minimizing the risk for coke formation. Moreover, as methanol can be produced from renewable sources, its reforming does not contribute to a net addition of CO2 to the atmosphere. Consequently, there are three processes available for H2 production using methanol as a H2 source: Steam reforming of methanol (SRM-endothermic reaction) CH3 OH þ H2 O / CO2 þ 3H2 (1) 2. 2.1. 2.1.1. Experimental Preparation of catalytic materials Support Partial oxidation of methanol (POM-exothermic reaction) CH3 OH þ 1=2O2 / CO2 þ 2H2 (2) ZrO2 was prepared by a sol–gel method from Zirconium(IV) propoxide (Fluka) as a precursor in n-propanol (Aldrich) solution and acid catalyst (HNO3–Baker) with constant stirring. The solution was processed at room temperature, and the deionized water was added dropwise to complete hydrolysis. The molar ratio used for the synthesis was: propoxide/ alcohol/H2O/HNO3 ¼ 1:4:4:0.33 [18]. After the hydrolysis reaction the temperature was increased at reflux and held for 50 min, then cooled at room temperature. The mixture was aged for 24 h and the residual liquid was removed by decanting. A xerogel was obtained after heating at 100  C for 24 h. The xerogel was first heated 1 h at 100  C under an air stream and then calcined at 650  C for 5 h. Oxidative Steam Reforming of Methanol (OSRM is a combination of SRM and POM) CH3 OH þ 1=2H2 O þ 1=4O2 / CO2 þ 5=2H2 (3) 2.1.2. Catalysts preparation by deposition–precipitation with urea One gram of ZrO2 was added to 100 ml of an aqueous solution at pH z 2 and 4.2 M of urea with constant stirring. Cu(CH3CO2)2$H2O (Merck) or NiCl2$6H2O at an appropriate concentration was incorporated at the suspension to yield 3 wt% of copper and nickel, respectively, in the monometallic catalysts. For bimetallic sample the concentration of Ni and Cu was 1.5 wt% of each one of the metal to obtain 3 wt% of total metallic phase. The temperature of the suspension was increased at 80  C for 20 h, and as the urea was decomposed the pH was increased. Then the solids were recovered by centrifugation and washed with deionized water and centrifuged again. This procedure was repeated 4 times. After that, the solids were dried at 100  C for 24 h. The catalysts were calcined as follows: at 100  C for 1 h and then the temperature was increased at 300  C for 2 h in air and cooled at room temperature, next, the catalysts were reduced with H2 (5%)/He (60 ml/min) at 600  C for 2 h. The actual Cu and Ni contents were determined by ICP and they were 2.80% of Cu in Cu/ZrO2 catalyst, 2.44% of Ni in the Ni/ZrO2 catalyst, and for bimetallic Cu–Ni/ZrO2 sample the Cu and Ni were 1.47 and 1.03%, respectively. In the literature, copper based catalysts have received considerable attention for H2 production by SRM [2–5]. Other catalysts that have been extensively studied in the important reforming industrial process for syngas production are nickel-based catalysts; this reaction also allows the conversion of two undesirable greenhouse gases like CH4 and CO2 [6–8]. However, the studies related with Ni-catalysts in the steam reforming of liquid products mainly used ethanol (SRE) as an H2 source [9–13]. Oxidative steam reforming of methanol has not been extensively studied, but initial results indicate low carbon monoxide and high hydrogen concentration in the products [14]. Velu et al. [15] studied the OSRM reaction and found that the ZrO2-containing catalysts are the best for H2 production with low CO levels. Agrell et al. [16] studied the SRM, POM and OSRM reaction and found in the OSRM reaction low CO levels with the following selectivity toward H2: SRM > OSRM > POM. They observed that the addition of O2 to the SRM reaction appears to be an effective way to decrease the CO content in the product. Navarro et al. [17] studied the oxidative reforming of hexadecane over Ni and Pt catalysts supported on Ce/La-doped Al2O3. They found for both Ni and Pt catalysts, higher specific activity when active metals were supported on alumina modified with cerium and lanthanum. However, the catalytic activity and H2 selectivity observed on Ni-based catalysts were higher than on Pt-based catalysts. The goal of this work was to develop new inexpensive Cu/ ZrO2, Ni/ZrO2 and Cu-Ni/ZrO2 catalysts by deposition– precipitation for oxidative steam reforming of methanol to produce H2-rich gas at relatively lower temperature. Catalysts characterization included BET (N2 adsorption–desorption), SEM (Scanning Electron Microscopy), EDX (Energy Dispersive X-ray Spectroscopy), XRD (X-ray Diffraction), TEM (Transmission Electron Microscopy) and TPR (Temperature Programmed Reduction). 2.2. Characterization Total surface area was calculated by the BET method from N2 adsorption by the single point method using a N2 (30%)/He gas mixture, recorded at liquid nitrogen temperature in a RIG-100 multitask from ISR INC. X-ray diffraction (XRD) powder patterns were recorded in a Siemens D-5000 diffractometer, using Cu Ka (l ¼ 0.15406 nm). The morphology and chemical composition analysis of the samples were performed in a LVSEM (Low Vacuum Scanning Electron Microscopy) JEOL JSM5900LV fitted with an Energy Dispersive X-ray Spectrometer (OXFORD). The analysis was performed in equipment conditions of 20 kV and 20 Pa of pressure. The images were obtained with the backscattering electron signal. Before the analysis, the samples were fixed on an aluminum specimen holder with aluminum tape. A Transmission Electron international journal of hydrogen energy 33 (2008) 4569–4576 4571 Microscope (TEM) JEOL JEM 2010 with resolution point to point of 0.23 nm was used to determine the structure and lattice parameters of the metallic nanoparticles on the support. HRTEM and local chemical analysis of the bimetallic nanoparticles were carried out in a microscope JEM 2200FS with a resolution of 0.19 nm which has been fitted with an energy dispersive X-ray Spectrometer (NORAN). The chemical analysis was made using the Scanning Transmission Electron Microscopy (STEM)-EDX technique since the STEM mode led us obtain a better control of the small probe size (less than 1 nm of diameter). The samples were prepared in a solution with isopropanol and a drop was put on copper or gold grids. Temperature-programmed reduction (TPR) experiments were carried out on an automatic multitask unit RIG-100 from ISR INC equipped with a Thermal Conductivity Detector (TCD) with output to a computer. The oxidized catalyst (0.1 g) was placed in the reactor and purged with UHP Ar at room temperature and then the TPR measurement was performed using H2 (5%)/Ar gas mixture (30 ml/min). The temperature was increased at a rate of 10  C/min from room temperature to 700  C. The effluent gas was passed through silica gel to remove water before measuring the amount of hydrogen consumed during the reduction by the TCD. The signal was calibrated by 0.5 ml pulses of UHP H2 (5%)/Ar at the end of the experiment. After testing the catalytic reaction, the catalyst was cleaned by He stream (30 ml/min) for 30 min at 360  C and cooled at room temperature, after this the sample was purged with UHP Ar flow and the TPR was performed. SCO ð%Þ ¼ nCO2-out  100 nCO2-out þ nCOout þ CH4-out (5) The subscripts in and out indicate the inlet and the outlet concentrations of the reactants or products. 3. 3.1. Results and discussion Textural and structural properties 2.3. Catalytic reaction The steady-state activity in the oxidative steam reforming of methanol reaction was performed in a conventional fixedbed flow reactor (8 mm i.d.) using 0.1 g of the catalyst in a temperature range from 250 to 360  C with 4 h stabilization time at each temperature and atmospheric pressure, with a thermocouple in contact with the catalytic bed allowing the control of the temperature inside the catalyst on an automatic multitask unit RIG-100. The catalyst was first activated in a stream of H2 (5%)/He (60 ml/min) from room temperature to 300  C with a heating rate of 10  C/min and held at this temperature for 1 h. The catalyst was brought up to the reaction temperature in He and the reaction mixture was introduced. For the OSRM reaction, O2 (5%)/He mixture was used and the total flow rate was kept at 50 ml/min (GHSV ¼ 30,000 hÀ1 based on the total flow) and added by means of a mass flow controller (RIG-100) and bubbled through a tank containing mixture of water and methanol, the partial pressure of CH3OH, H2O and O2 was 75, 12.75 and 25.2 Torr, respectively. The effluent gas of the reactor was analyzed by gas chromatography using TCD. A 2-m packed Porapack Q column able to separate water, methanol, methyl formate (MF) and CO2 was used. The gaseous products such as H2, O2, CH4 and CO were separated with ˚ a molecular sieve of 5 A. The following equations were used to determine the methanol conversion and selectivity: Cin À Cout  100; Cin nH2-out SH2 ð%Þ ¼  100 nH2-out þ nCH4-out þ nH2 Oout Xð%Þ ¼ The surface area calculated by the BET method from N2 adsorption–desorption by the single point method of the bare ZrO2 was 30 m2/g, after the incorporation of the active phase on the ZrO2 support, the surface area was slightly increased to 33, 34 and 35 m2/g for Cu/ZrO2, Ni/ZrO2 and Cu– Ni/ZrO2 catalysts, respectively. This slight increment of the surface area could be attributed to the partial dissolution of the ZrO2 support by the acid medium when the active phase was impregnated. During the centrifuged, drying and thermal treatments the dissolved material would be reprecipitated as smaller particles, so accounting for the increase in the surface area. Fig. 1 shows the experimental XRD patterns of the Cu/ ZrO2 and Ni/ZrO2 catalysts. Diffraction pattern of metallic copper and nickel as well as diffraction peaks of the monoclinic ZrO2 phase were observed. Cu, Ni or Cu–Ni alloy were not observed by XRD in the Cu–Ni/ZrO2 catalyst. After catalytic reaction, the Cu–Ni/ZrO2 sample showed a similar diffraction pattern to the pre-reaction catalyst. The morphology of the three catalysts was analyzed by LVSEM and a typical image of the Cu–Ni/ZrO2 catalyst, is illustrated on Fig. 2. All the samples studied exhibited nanoparticles approximately 150 nm contained in large spongy clusters. However, nanoparticles with semispherical morphology approximately 10 nm of diameter deposited on the surface of the ZrO2 crystalline were revealed by TEM technique. Ni nanoparticles of w10 nm of diameter were observed on the Ni/ZrO2 catalyst (Fig. 3a). Fig. 3b shows the TEM results of the bimetallic Cu–Ni/ZrO2 sample. The bright field STEM image of the Cu–Ni/ZrO2 catalyst shows good dispersion of l l l l ll l l ll Ni/ZrO2 * ll l l l l l l ll l l l l Intensity (a.u.) x2 Cu-Ni/ZrO2 rxn °* Cu-Ni/ZrO2 ° 20 30 40 50 60 70 Cu/ZrO2 80 90 2 (theta) ð4Þ Fig. 1 – XRD patterns of the Cu/Ni/ZrO2 catalysts before and after catalytic activity. (l)-monoclinic-ZrO2, (B)-Cu, (*)-Ni. 4572 international journal of hydrogen energy 33 (2008) 4569–4576 Fig. 2 – SEM image of the fresh bimetallic Cu–Ni/ZrO2 catalyst. the metal-containing nanoparticles. These images seem to indicate a bimodal size distribution with a large grouping of particles around 10 nm. In order to elucidate the chemical composition of these nanoparticles the EDX analysis was performed on it. Inset EDX spectrum in Fig. 3b, carried out in the nanoparticles with 10 nm of diameter, clearly showed the presence of Cu and Ni elements. These results reveal the bimetallic nature of this system and they have the following composition: 18% of the nanoparticles have a Ni/Cu w 4.6, 41% have a Ni/Cu w 1.7, 29% have a Ni/Cu w 1, 6% have a Ni/ Cu w 0.6 and 6% have a Ni/Cu w 0.25 weight ratio, respectively. Cu nanoparticles on the Cu/ZrO2 catalyst were not found during the TEM analysis, however, it was present in the samples as was identified by EDX analysis, inset spectrum in Fig. 3c. 3.2. Temperature-programmed reduction closer to the monometallic Cu/ZrO2 catalyst but far from the reduction peak observed on Ni/ZrO2 sample. This study clearly exhibits differences in the interactions between Cu/Ni species on the surface of the zirconia when they are together, and could be explained as follows: during the TPR test, Cu probably causes spillover of hydrogen onto the Ni inducing a concurrent reduction of both copper oxide and NiO. For that, the presence of Cu lowered the reduction temperature of Ni. A similar result was reported by Arenas-Alatorre et al. [23] in the TPR experiments on the Pt–Ni/SiO2 catalysts, they observed that the presence of the Pt in the bimetallic catalysts contributes to facilitate the reduction of the NiO. On the other hand, Vizcaıno ´ et al. [24] in the bimetallic Cu–Ni/SiO2 catalyst reported reduction peaks between 200 and 260  C. The peak at low temperature was assigned to CuO reduction and the other was attributed to NiO reduction. A detailed analysis of TPR profile and the results of TEM and HRTEM techniques suggested that the first reduction peak of the bimetallic catalyst could be attributed to the reduction of adjacent Cu and Ni atoms, which could be forming a bimetallic phase. The second reduction peak could be assigned to the remaining Ni atoms forming Ni-rich nanoparticles. This proposal could be supported with the results from HRTEM technique. Fig. 5 shows HRTEM image of a nanoparticle deposited on the zirconia support from Cu– Ni/ZrO2 catalyst. The atomic interplanar distance measured in the nanoparticle was 0.207 nm which corresponds to the cubic system of the bimetallic Cu0.81Ni0.19 phase in (111) plane with the unit cell parameter a ¼ 0.3593 nm according to the JCPDS card number 471406. Chemical analysis carried out by EDX revealed strongly Cu and Ni elements. Samples’ post-reaction also was characterized by TPR technique, and their experimental profiles show a tiny broad H2 consumption at low temperatures with long tail extending to higher temperature than fresh catalysts. These results suggest that the gas stream causes small oxidation in the active phase having highly dispersed nickel and copper oxides species on the catalysts at w220–300  C and 200  C, respectively [2,22,25–29]. Fig. 4 shows the TPR profiles of the fresh Cu/Ni/ZrO2 catalysts calcined at 300  C and the samples after catalytic reaction. Reduction peaks observed on the catalysts at temperatures below 350  C were associated to the reduction of CuO and NiO particles. The peak above 500  C observed on the three samples is related to the reduction of hydroxycarbonates species (identified by FTIR, Figure not shown) which originate from the urea decomposition during the synthesis of the samples and remain present on the surface after calcinations. TPR profile of the fresh NiO/ZrO2 sample shows a peak at 320  C indicating that NiO is reduced to metallic Ni. Literature reports that large NiO particles with lower interaction with the ZrO2 on the Ni/ZrO2 catalyst could be reduced at low temperature [19–21]. The reduction of CuO supported on ZrO2 shows two peaks at 200 and 250  C indicating the existence of two different kinds of CuO species. Highly dispersed copper oxide and CuO bulk were present on the Cu/ZrO2 sample [22]. TPR profile of the bimetallic catalyst showed a similar behavior like on the fresh Cu/ZrO2 sample, although Ni was also present on the catalyst. On this sample a shoulder at 212 and a peak at 225  C were observed, these temperatures are 3.3. Catalytic performance on the oxidative steam reforming of methanol (OSRM) reaction Fig. 6 shows the catalytic behavior of Cu/Ni/ZrO2 catalysts during OSRM reaction at different temperatures. In the Cu/ ZrO2 catalyst, the conversion of methanol was 11% at the beginning of the reaction (250  C) and increased as temperature was raised, and at 300  C the consumption of methanol was w50%. Additional temperature increase did not result in an increase in methanol conversion. However, when copper was supported on ceria, 100% of methanol conversion at 260  C was reported on catalysts with <6% of copper [25]. This effect is caused by the modification in feed concentrations of fuel, oxygen or steam [30]. On the Ni/ZrO2 sample, the conversion of methanol in the range of 250–300  C was <14%. After this temperature the methanol conversion ´ reached w100% at 350  C. Vizcaıno et al. [24] reported a similar behavior during SR of ethanol reaction. They observed high catalytic activity on Ni/SiO2 sample than Cu/SiO2 catalyst. In the case of the bimetallic Cu–Ni/ZrO2 catalyst, the catalytic activity was higher than the monometallic samples in almost international journal of hydrogen energy 33 (2008) 4569–4576 4573 Fig. 3 – TEM image of: (a) Ni/ZrO2, (b) bright field STEM image of the Cu–Ni/ZrO2, (c) Cu/ZrO2 catalysts. all ranges of the reaction temperature with nearly complete conversion reached by 350  C. In the literature there are no studies associated with the steam reforming of methanol reaction on the bimetallic Cu–Ni catalysts. However, some reports related with the catalytic activity of the bimetallic Ni–Cu catalysts in the steam reforming (SR) and oxidative steam reforming (OSR) have been done only with ethanol [11,12,31]. Gallucci et al. [32] reported that the SR of methanol is more suitable than SR of ethanol for hydrogen production. Marino et al. [11,12] studied the effect of the nickel content ˜ in the Cu/Al2O3 samples on the steam reforming of ethanol reaction. They found that the conversion of the catalysts improves when nickel content increases. This behavior was attributed to the addition of Ni which favors the segregation of Cu2þ ions to the catalytic surface and enhances the ethanol conversion. In other report, the catalytic activity was related with the high metal dispersion [26]. In our case, besides the dispersion and segregation of metallic ions, the best catalytic activity observed in the Cu–Ni/ZrO2 sample was associated to the presence of the bimetallic phase nanoparticles on the zirconia support. Because of the Cu/ZrO2 and Ni/ZrO2 catalysts only Cu or Ni nanoparticles were identified, and their catalytic activity was lesser at low temperatures than in bimetallic catalyst. Thus the bimetallic alloy of the two metals can be used efficiently as an active phase during OSRM reaction. In addition, the bifunctional role of the bimetallic phase with the ZrO2 had an important function in the catalytic activity. Agrell et al. [16] reported that Cu/ZnO/ZrO2 catalyst exhibits high activity for methanol conversion due to the high Zr/Cu ratio which favors the possible copper-support interaction increasing the bifunctional role between the active phases and the ZrO2 beneficial for the reaction, in addition zirconia 4574 international journal of hydrogen energy 33 (2008) 4569–4576 245 306 320 Ni/ZrO2 post-reaction 550 100 Methanol conversion (%) H2 Consumption (a.u.) Ni/ZrO2 80 60 40 20 0 250 Cu/ZrO2 Cu-Ni/ZrO2 Ni/ZrO2 187 212 177 200 250 100 200 300 225 Cu-Ni/ZrO2 post-reaction Cu-Ni/ZrO2 550 Cu/ZrO2 post-reaction Cu/ZrO2 571 400 500 600 270 290 310 330 350 Temperature (°C) Fig. 4 – Temperature-programmed reduction profiles of the fresh catalysts (solid line), samples after catalytic reaction (thin line). Temperature °C Fig. 6 – Effect of temperature on the catalytic performance in the oxidative steam reforming of methanol over Cu/Ni/ ZrO2 catalysts. Partial pressure of CH3OH, H2O and O2 was 75, 12.75 and 25.2 Torr, respectively. GHVS [ 30,000 hL1. avoids the deactivation of the catalyst by coke deposition during the reaction and formation of CO. It is worth noting a better correlation between catalytic conversion and the reduction of the samples at low temperature. In this case the most active catalysts had the lower temperature reduction peaks. The main products of the OSRM reaction from Cu/Ni/ZrO2 catalysts were H2, CO, CO2 and H2O. A few quantity of methyl formate as by-product of the reaction was observed in three samples. Methane was also produced in small amount on the Ni/ZrO2 and Cu–Ni/ZrO2 catalysts. Fig. 7 showed the distribution of hydrogen on the Cu/Ni/ZrO2 catalysts and it could be produced by means of Eqs. (6)–(10) and (12). The selectivity of the Cu/ZrO2 catalyst at 250  C was w30% and 0% for the other samples. When the temperature was increased up to 300  C it was observed that the H2 selectivity was also increased, after this temperature it remained essentially unchanged on the three samples. However, it can be observed that the methanol conversion increased after 300  C on the Ni-based catalysts (Fig. 6) but the H2 did not raise, this result could be explained by the oxidation of the H2 with O2 (Eq. (13)) [25] or another possibility by means of Eq. (14). Thus stable hydrogen productions over 60% were obtained for the Cu/Ni/ZrO2 catalysts. At the beginning of the reaction all samples showed high CO2 selectivity, Fig. 8. However, as the reaction temperature increases from 250 to 350  C the CO2 production decreases, this effect could be correlated by rWGS reaction (Eq. (14)) in the Ni-content samples. Nevertheless, another possibility to obtain CO as by-product of the reaction is from methanol decomposition at higher temperatures (Eq. (15)), so CO2 production decreases. Between them, the catalyst which showed high methanol conversion also had faster drop in the CO2 selectivity than the other samples. However, on the monometallic Cu/ZrO2 catalyst only w10% of CO2 was lost at 100 H2 Selectivity (mol %) 80 60 40 20 0 250 Cu/ZrO2 Cu-Ni/ZrO2 Ni/ZrO2 270 290 310 330 350 Temperature (°C) Fig. 7 – H2 selectivity as a function of reaction temperature. Partial pressure of CH3OH, H2O and O2 was 75, 12.75 and 25.2 Torr, respectively. GHVS [ 30,000 hL1. The other H containing product was the water and methane. Fig. 5 – HRTEM image of bimetallic nanoparticle deposited on the zirconia of the Cu–Ni/ZrO2 catalyst. international journal of hydrogen energy 33 (2008) 4569–4576 4575 100 CO2 Selectivity (mol %) sequence of the reactions can be summarized during OSRM reaction over these Cu/Ni/ZrO2 catalysts: 2CH3 OH þ OðaÞ / CH3 OCHO þ H2 O þ H2 (6) 80 60 2CH3 OH / CH3 OCHO þ 2H2 40 20 0 250 Cu/ZrO2 Cu-Ni/ZrO2 Ni/ZrO2 270 290 310 330 350 (7) CH3 OCHO / 2CO þ 2H2 (8) CH3 OH þ 2OHðaÞ / CO2 þ H2 O þ 2H2 (9) Temperature (°C) Fig. 8 – CO2 selectivity as a function of reaction temperature. Partial pressure of CH3OH, H2O and O2 was 75, 12.75 and 25.2 Torr, respectively. GHVS [ 30,000 hL1. CH3 OH þ OHðaÞ / CO þ H2 O þ 3=2H2 (10) CH3 OCHO / CH4 þ CO2 the maximum reaction temperature. Fig. 9 shows the CO selectivity of the three catalysts. The CO2 depletion observed on Fig. 8 essentially on the Ni-content samples is due to the change in the selectivity toward CO production, and it can be produced by following Eqs. (8), (10), (12), (14) and (15). Because Ni/ZrO2 catalyst had high CO selectivity in the OSRM reaction, the higher CO production observed on the Cu–Ni/ZrO2 sample could be associated at the presence of bimetallic Ni-rich nanoparticles as was identified by TEM– EDX during the study. In addition, the presence of copper on bimetallic sample reduces the CH4 formation. Selectivity toward CH4 is presented in Fig. 9 and could be formed by means of Eq. (11). According to the results and reports on the literature [24,33] the role of our catalysts in the OSRM reaction is: the major reaction intermediates are located on the zirconia while the role of copper and nickel active phase is to promote hydrogen spillover and then release to the feed gas. It is clear that during OSRM reaction, Ni-based catalysts produces relatively high concentration of CO in special on the bimetallic sample, which is still much higher than the upper limit of CO concentration in the feed gas for PEM fuel cells. Thus, the integrated catalyst system with a suitable function that promoted both OSRM and WGS reactions should be developed. The following 100 80 60 40 20 0 250 CH4 270 290 310 330 350 (11) CH4 þ H2 O 4 CO þ 3H2 (12) H2 þ 1=2O2 / H2 O (13) CO2 þ H2 / CO þ H2 O (14) CH3 OH / CO þ 2H2 (15) 4. Conclusions CO, CH4 Selectivity (mol %) Cu/ZrO2 Cu-Ni/ZrO2 Ni/ZrO2 Temperature (°C) Fig. 9 – CO and CH4 selectivity as a function of reaction temperature. Partial pressure of CH3OH, H2O and O2 was 75, 12.75 and 25.2 Torr, respectively. GHVS [ 30,000 hL1. In the present study, Cu/ZrO2, Ni/ZrO2 and Cu–Ni/ZrO2 catalysts have been developed for oxidative steam reforming of methanol to produce H2-rich gas at relative lower temperature. The TPR results revealed two different kinds of CuO: (i) highly dispersed CuO species and CuO bulk present on the CuO/ZrO2 catalyst and (ii) free NiO ,i.e., with no metal-support interactions or highly dispersed NiO particles was evidenced in the NiO/ZrO2 sample. The presence of Cu in the bimetallic catalyst facilitates the reduction of Ni at lower temperatures. Copper and nickel metallic nanoparticles on Cu/ZrO2 and Ni/ ZrO2 catalysts were observed by TEM, while bimetallic nanoparticles with different Cu/Ni weight ratios were identified on the Cu–Ni/ZrO2 sample. The steady-state activity showed that the Ni-based catalyst was more effective than the Cubased sample when was supported on ZrO2 for the OSRM reaction at higher temperatures, indicating that Ni-based catalysts is better for this reaction. The Cu–Ni/ZrO2 catalyst showed the best catalytic performance at low temperatures than the monometallic samples. This behavior was attributed to the bimetallic nanoparticles present on the surface of the catalyst that improves the bifunctional effect between the active bimetallic phase and the support during the OSRM reaction. All the catalysts showed the same selectivity toward H2 at the maximum reaction temperature and it was w60%. The high selectivity toward CO observed on the Cu–Ni/ZrO2 sample is associated to the presence of the Ni-rich bimetallic nanoparticles, as evidenced by TEM and EDX analysis, since 4576 international journal of hydrogen energy 33 (2008) 4569–4576 this behavior is similar to the one showed by the monometallic Ni-catalyst. Acknowledgements ´ ´ Thanks to I.Q. Albina Gutierrez Martınez, Jorge Perez and Luis ´ ´ Rendon for technical support and to the project ININ-CA-711 and CONACYT J-48924 for financial support. references [1] Olah GA. After oil and gas: methanol economy. Catal Lett 2004;93:1–2. [2] Yao C-Z, Wang L-C, Liu Y-M, Wu G-S, Cao Y, Dain W-L, et al. Effect of preparation method on the hydrogen production from methanol steam reforming over binary Cu/ZrO2 catalysts. Appl Catal A: Gen 2006;297:151–8. [3] Szizybalski A, Girgsdies F, Rabis A, Wang Y, Niederberger M, Ressler T. In situ investigations of structure–activity relationships of a Cu/ZrO2 catalyst for the steam reforming of methanol. J Catal 2005;233:297–307. [4] Lindstrom B, Pettersson LJ. Hydrogen generation by steam reforming of methanol over copper-based catalysts for fuel cell applications. Int J Hydrogen Energy 2001;26:923–33. [5] Purnama H, Girgsdies F, Ressler T, Schattka J-H, Caruso RA, Scomacker R, et al. Activity and selectivity of ¨ a nanostructured CuO/ZrO2 catalyst in the steam reforming of methanol. Catal Lett 2004;94:61–8. [6] ACW Koh, Chen L, Leong WK, Johnson BFG, Khimyak T, Lin J. Hydrogen or synthesis gas production via the partial oxidation of methane over supported nickel–cobalt catalysts. Int J Hydrogen Energy 2007;32:725–30. [7] Venugopal A, Naveen Kumar S, Ashok J, Hari Prasad D, Durga Kumari V, Prasad KBS, et al. Hydrogen production by catalytic decomposition of methane over Ni/SiO2. Int J Hydrogen Energy 2007;32:1782–8. [8] Liu Y, Liu D. Study of bimetallic Cu–Ni/g-Al2O3 catalysts for carbon dioxide hydrogenation. Int J Hydrogen Energy 1999; 24:351–4. [9] Yang Y, Ma J, Wu F. Production of hydrogen by steam reforming of ethanol over a Ni/ZnO catalyst. Int J Hydrogen Energy 2006;31:877–82. [10] Biswas P, Kunzru D. Steam reforming of ethanol for production of hydrogen over Ni/CeO2–ZrO2 catalyst: effect of support and metal loading. Int J Hydrogen Energy 2007;32: 969–80. [11] Marino FJ, Cerrella EG, Duhalde S, Jobbagy M, Lombarde M. ˜ Hydrogen from steam reforming of ethanol. Characterization and performance of copper–nickel supported catalysts. Int J Hydrogen Energy 1998;23:1095–101. [12] Marino FJ, Boveri M, Baronetti G, Lombarde M. Hydrogen ˜ production from steam reforming of bioethanol using Cu/Ni/ K/g-Al2O3 catalysts. Effect of Ni. Int J Hydrogen Energy 2001; 26:665–8. [13] Sun J, Qui X-P, Wu F, Zhu W-T. H2 from steam reforming of ethanol at low temperature over Ni/Y2O3, Ni/La2O3 and Ni/ Al2O3 catalysts for fuel-cell application. Int J Hydrogen Energy 2005;30:437–45. [14] Velu S, Suzuki K, Osaki T. Oxidative steam reforming of methanol over Cu/ZnAl(Zr)-oxide catalysts; a new and efficient method for the production of CO-free hydrogen for fuel cells. Chem Commun 1999:2341–2. [15] Velu S, Suzuki K, Okazaki M, Kapoor MP, Osaki T, Ohashi F. Oxidative steam reforming of methanol over CuZnAl(Zr)oxide catalysts for the selective production of hydrogen for fuel cells: catalyst characterization and performance evaluation. J Catal 2000;194:373–84. ´ [16] Agrell J, Birgersson H, Boutonnet M, Melian-Cabreara I, Navarro RM, Fierro JLG. Production of hydrogen from methanol over Cu/ZnO catalysts promoted by ZrO2 and Al2O3. J Catal 2003;219:389–403. ´ ´ [17] Navarro RM, Alvarez-Galvan MC, Rosa F, Fierro JLG. Hydrogen production by oxidative reforming of hexadecane over Ni and Pt catalysts supported on Ce/La-doped Al2O3. Appl Catal A: Gen 2006;297:60–72. ´ ´ ´ ´ [18] Perez-Hernandez R, Aguilar F, Gomez-Cortes A, Dıaz G. NO ´ reduction with CH4 or CO on Pt/ZrO2–CeO2 catalysts. Catal Today 2005;107–108:175–80. [19] Montoya JA, Romero-Pascual E, Gimon C, Del Angel P, ´ Monzon A. Methane reforming with CO2 over Ni/ZrO2–CeO2 catalysts prepared by sol–gel. Catal Today 2000;63:71–81. [20] Shan W, Luo M, Lin P, Shen W, Li C. Reduction property and catalytic activity of Ce1ÀxNixO2 mixed oxide catalysts for CH4 oxidation. Appl Catal A: Gen 2003;246:1–9. [21] Kirumakki SR, Shpeizer BG, Sagar GV, Chary KVR, Clearfield A. Hydrogenation of Naphthalene over NiO/SiO2– Al2O3 catalysts: structure–activity correlation. J Catal 2006; 242:319–31. [22] Ratnasamy P, Srinivas D, Satyanarayana CVV, Manikandan P, Senthil Kumaran RS, Sachin M, et al. Influence of the support on the preferential oxidation of CO in hydrogen-rich steam reformates over the CuO–CeO2–ZrO2 system. J Catal 2004;221:455–65. ´ ´ [23] Arenas-Alatorre J, Gomez Cortes A, Avalos Borja M, Dıaz G. ´ Surface properties of Ni–Pt/SiO2 catalysts for N2O decomposition and reduction by H2. J Phys Chem B 2005; 109(6):2371–6. [24] Vizcaıno AJ, Carrero A, Calles JA. Hydrogen production by ´ ethanol steam reforming over Cu–Ni supported catalysts. Int J Hydrogen Energy 2007;32:1450–61. ´ ´ ´ ´ [25] Perez-Hernandez R, Gutierrez-Martınez A, Gutierrez´ Wing CE. Effect of Cu loading on CeO2 for hydrogen production by oxidative steam reforming of methanol. Int J Hydrogen Energy 2007;32:2888–94. [26] Kugai J, Subramani V, Song C, Engelhard MH, Chin Y-H. Effects of nanocrystalline CeO2 supports on the properties and performance of Ni–Rh bimetallic catalyst for oxidative steam reforming of ethanol. J Catal 2006;238:430–40. [27] Molina R, Poncelet G. a-Alumina-supported nickel catalysts prepared from nickel acetylacetonate: a TPR study. J Catal 1998;173:257–67. [28] Frusteri F, Freni S, Chiodo V, Donato S, Bonura G, Cavallaro S. Steam and auto-thermal reforming of bio-ethanol over MgO and CeO2 Ni supported catalysts. Int J Hydrogen Energy 2006; 31:2193–9. [29] Arena F, Licciardello A, Parmaliana A. The role of Ni2þ diffusion on the reducibility of NiO/MgO system: a combined TRP–XPS study. Catal Lett 1990;6:139–49. [30] Ahmed S, Krumpelt M. Hydrogen from hydrocarbon fuels for fuel cells. Int J Hydrogen Energy 2001;26:291–301. [31] Marino F, Boveri M, Baronetti G, Lombarde M. Hydrogen ˜ production via catalytic gasification of ethanol. A mechanism proposal over copper–nickel catalysts. Int J Hydrogen Energy 2004;29:67–71. [32] Gallucci F, Basile A, Tosti S, Iulianelli A, Drioli E. Methanol and ethanol steam reforming in membrane reactors: an experimental study. Int J Hydrogen Energy 2007;32:1201–10. [33] Fisher IA, Bell AT. A mechanistic study of methanol decomposition over Cu/SiO2, ZrO2/SiO2, and Cu/ZrO2/SiO2. J Catal 1999;184:357–76.