Applied Catalysis A: General 299 (2006) 285291 www.elsevier.

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Remarkable support effect for liquid phase methanol reforming with water over supported PtRu catalysts
Toshihiro Miyao, Masaya Yamauchi, Hiroaki Narita, Shuichi Naito *
Department of Applied Chemistry, Faculty of Engineering, Kanagawa University, 3-27-1, Rokkakubashi, Kanagawa-ku, Yokohama 221-8686, Japan Received 8 July 2005; received in revised form 21 October 2005; accepted 26 October 2005 Available online 2 December 2005

Abstract Support effect for the catalytic activity of liquid phase reforming of methanol with water was investigated over various supported PtRu bimetallic catalysts. The SiO2, TiO2, Al2O3, MgO, CeO2 and ZrO2 were used as support materials by conventional impregnation method. Basic oxide supports improved the selectivity to CO2, whereas acidic supports suppressed the catalytic activity and selectivity. The PtRu/TiO2 catalyst exhibited highest activity and selectivity for CO2, which were improved by higher temperature reduction. The improved activity and selectivity were attributable to the occurrence of SMSI state and PtRu alloy, respectively. The reforming reaction over PtRu/TiO2 catalyst proceeded through partially dehydrogenated HCOOCH3 and HCOOH intermediate with the similar mechanism as that over SiO2 supported PtRu catalyst. # 2005 Elsevier B.V. All rights reserved.
Keywords: Liquid phase reforming of methanol; Hydrogen production; Support effect; PtRu/TiO2 catalyst

1. Introduction The development of efcient techniques for hydrogen production will be crucial to establishing hydrogen as a fuel of the future. A chemical conversion of methanol is one of the most promising methods because of its easy conversion, storage and handling with relatively low prices. The most popular process of hydrogen production from methanol is a steam reforming, which have been studied extensively and reported that Cu and group VIII metal catalysts showed excellent activity for the reaction [1]. For example, Cu/ZnO catalyst is well known to show the highest activity at higher temperatures, but still insufcient for lower temperature reforming which is more favorable to fuel cell processes. On the other hand, supported VIII group metal catalysts exhibited higher activity at lower temperature reforming, but decomposition reaction of methanol took place simultaneously forming signicant amount CO [1]. A liquid phase reforming of methanol is one of the promising solutions for designing new process of hydrogen

* Corresponding author. Tel.: +81 45 481 5661; fax: +81 45 491 7915. E-mail address: naitos01@kanagawa-u.ac.jp (S. Naito). 0926-860X/$ see front matter # 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.apcata.2005.10.043

production. As compared with the usual steam reforming reaction, the advantages of liquid phase reforming are making more compact and simple reaction equipment and needless of the evaporation energy of methanol aqueous solution. In spite of its importance, there are few researches that dealt with the liquid phase reaction from a viewpoint of heterogeneous catalysis except for an anodic reaction in DMFC [2,3]. Fujii and Saito studied a hydrogen evolution from methanol by using homogeneous ruthenium catalysts [4]. The study for liquid phase reactions of methanol and other oxygenated hydrocarbons with water was reported over supported Pt catalysts at 500 K [5,6]. From their reports, Pt/TiO2 catalyst is the most active catalyst for the production of hydrogen whereas lower catalytic activity is exhibited by Pt supported on CeO2, ZnO and SiO2 [6]. Okamoto et al. investigated liquid phase reforming of methanol over Cu/ZnO catalyst at 500 K and reported that, over the catalyst in a batch reactor, a selectivity to CO2 was more than 99% [7]. However, these studies are performed relatively high pressures (around 10 MPa) and temperatures (above 500 K). We aimed the hydrogen manufacture process by the liquid phase methanol reforming reaction in moderate conditions. In the investigation of DMFC, Pt is known as the most active element as the catalysts for dehydrogenation of

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methanol. But Pt itself is not sufciently active to be useful commercially. The simplest method of promotion of the catalytic activity is the use of alloying of Pt with different metals, i.e. PtSn, PtRu, PtOs, PtIr, etc. [3]. It is widely accepted that PtRu alloy is the most active catalyst for the activation of methanol. The other method for promotion is a combination of Pt with a base metal oxide, especially the groups IVVI transition metal oxides. Among them, WOx [18,20], VOx, MoOx [19] and TiO2 [9,21,22] were reported to promote catalytic activities of Pt or PtRu anode catalyst for the anodic oxidation of methanol. Shen and Tseung investigated Pt/WO3 electrode for DMFC claimed that the advantages of using Pt/WO3 catalytic electrodes would be the continuous formation and oxidation of tungsten bronze and active for the oxidation of poisons, such as CO, since water adsorbed on the tungsten trioxide [18]. Lasch et al. reported the improvement of the catalytic activity towards methanol oxidation by the addition of WOx, MoOx and VOx to PtRu electrode [19]. Otomo et al. investigated electro-catalytic activity of Pt/TiO2 catalyst for the anodic methanol oxidation. From their reports, the interaction between Pt and CO is weaker on TiO2 than on conventional carbon supported Pt anode [9]. We have studied the liquid phase reforming of methanol with water over silica supported Pt-group catalyst in the batch reactor with suspended powder catalyst at boiling point of the methanol solution. The main purpose of our study is the development of more simple and compact system for production of pure hydrogen [8,17]. In our study on the methanol reforming reaction, PtRu/SiO2 catalyst exhibited much higher activity than Pt/SiO2 and Ru/SiO2 catalysts. The formation of solid solution of Pt and Ru by the addition of Ru to the Pt/SiO2 catalyst improved a CO tolerance capacity remarkably. The reforming reaction over PtRu/SiO2 catalyst proceeded through HCOOCH3 and HCOOH, and the dehydrogenation of methanol is the rate determining step of the reaction. Although DMFC studies described above have been investigated by the half cell experiments at acidic conditions, it is strongly suggested that the catalytic activity of liquid phase methanol reforming by neutral conditions over suspended catalysts can be also improved by using of effective metal oxide to platinum group metal catalysts. In the present study, we have investigated liquid phase reforming reaction of methanol over PtRu metals supported on various oxides and the effect of support materials for catalytic activity and selectivity was discussed in depth. The reaction mechanisms over TiO2 supported PtRu catalyst was also investigated by a kinetic approach. 2. Experimental 2.1. Preparation of catalysts Supported PtRu catalysts were prepared by conventional impregnation method. SiO2 (Japan Aerosil, Aerosil300), Al2O3 (AL2O3, Japan Aerosil), MgO (Wako Pure Chemical), TiO2

(P-25, Japan Aerosil), ZrO2 (PX-81, TOSOH) and CeO2 (Anan Kasei, J-3) were used for support materials. These oxides used as a support were impregnated to an aqueous solution of H2PtCl66H2O (Wako Pure Chemical) and RuCl3nH2O (Wako Pure Chemical) followed by evaporation at 308 K and dried at 383 K for overnight. For all of the supported PtRu catalysts, the loading of Pt was adjusted to 5 wt.% and the molar ratio of Pt/Ru was unity. 2.2. Catalytic activity measurements The pretreatment of catalyst and the liquid phase reforming reaction of methanol were carried out in a Pyrex glass reactor (volume: 300 ml) with reux condenser connected to a closed gas circulation system. Gas phase products were analyzed by TCD gas chromatograph (GC-8A, Shimadzu) and liquid phase products were analyzed by FID gas chromatograph (GC-14B, Shimadzu). The 0.5 g of catalyst was placed in the reactor and then reduced under hydrogen ow atmosphere at 673 K, 40 kPa for 5 h. After the pretreatment of catalyst, 60 cm3 of degassed methanol solution (typically 10% CH3OH/H2O) was introduced into the reactor under nitrogen atmosphere by using Schlenk technique. Then the catalyst suspension of methanol solution was further degassed at liquid nitrogen temperature after then the reactor was heated with an oil bath until reux of the methanol solution started under vapor pressure and balanced nitrogen gas as a internal standard. The reaction experiments were performed usually between 350 and 357 K. 2.3. Characterization of catalysts A transmission electron microscope (JEM2010, JEOL) with an acceleration voltage of 200 kV and LaB6 cathode was applied for high resolution images of the supported catalysts. Samples were prepared by suspending the catalyst powder ultrasonically in 2-propanol and depositing a drop of the suspension on a standard copper grid covered with carbon monolayer lm. A X-ray photoelectron spectrometer (JPS9010, JEOL) with Mg Ka X-ray source (10 kV, 10 mA) was applied for chemical states of supported catalysts. Samples were prepared by molding in a thin disk shape and introduced into a pretreatment chamber. After reduction in hydrogen at 473 K the sample was transformed to the analysis chamber without exposure to air. The adsorption amount of hydrogen or CO over used catalysts was measured by a static volumetric adsorption apparatus (Omnisorp100CX, Beckmann Coulter) at 298 K. Before measurement, the used catalysts were dried at room temperature and reduced at 473 K for 3 h in a ow of hydrogen at atmospheric pressure. A rst adsorption isotherm was achieved so as to measure the total amount of adsorbed gases. The catalyst was then evacuated at 298 K for 1 h and a second adsorption isotherm was measured. The dispersion (D (%); percentage of metal atoms exposed to the surface) of supported metal was evaluated from the amount of total chemisorbed H2 and an adsorption stoichiometry (H/metal atom).

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catalysts corresponding to the reaction stoichiometry described below: CH3 OH H2 O 3H2 CO2 : In Table 1, the catalytic activity and selectivity over various supported PtRu catalysts were summarized with the values of metal dispersion (D, %). The selectivity to CO2 was calculated according to the formula shown as follows; SCO2 = CO2/ (CO2 + CO) 100%. The activity and selectivity were greatly affected by the kinds of support employed. On the basis of turnover frequency determined by the amount of H2 chemisorption, PtRu/Al2O3, PtRu/MgO and PtRu/ZrO2 catalysts exhibited lower TOF of hydrogen formation. On the contrary, PtRu/TiO2 exhibited much higher activity (6.4 104 s1) and selectivity (90.9%) than the other catalysts. It is worth noticing that PtRu catalysts supported on basic supports such as MgO, TiO2 and ZrO2 exhibited higher selectivity toward CO2 formation in the methanol reforming reaction. The poor selectivity of PtRu/Al2O3 suggested that acidic property has a negative effect for the CO2 formation. Over acidic supports, further dehydrogenation of partially dehydrogenated intermediates may take place to form CO. Over PtRu/CeO2 catalyst, large amount of hydrogen was formed at the initial stage of the reaction accompanied with the signicant decrease of the H2 formation rate, which may be explained by the oxidation of partially reduced ceria. Hamnett et al. investigated addition effect of WOx, ZrOx and TiOx on the catalytic activity for methanol oxidation [21]. They claimed the formation of PtTi oxide complex and explained the improvement of the electro-oxidation rate of methanol by the oxidation of PtCHO or Pt3HBBCOH residues to CO2. Machida et al. investigated addition of tungsten bronze (Ln0.1WO3; Ln = rare earth) to Pt electrode for methanol oxidation. They reported that the Pt/Ln0.1WO3 exhibited a much higher activity toward electro-oxidation of CH3OH in the presence of CO as compared with ordinary Pt electrodes because the WO3/WO3+ redox couple existed and removed adsorbed CO on Pt [20]. Similar process may take place on our catalysts, and it is suggested that the activation of water molecules proceeds on TiO2 support, which oxidize the methanol intermediates adsorbed on Pt sites. The importance

Fig. 1. Time courses of liquid phase reforming of methanol with water at 350 K over TiO2 or SiO2 supported PtRu catalyst.

3. Results and discussion 3.1. Methanol reforming reaction over various supported PtRu catalysts Fig. 1 shows the time courses of products formation during liquid phase methanol reforming with water at 353 K over PtRu/TiO2 and PtRu/SiO2 where H2 and CO2 were the major products with a small amount of CO. Over TiO2 supported catalyst, hydrogen was linearly produced for a longer reaction period whose amount reached to 800 mmol after 300 min. The hydrogen formation rate after 300 min over TiO2 supported catalyst was twice as large as that over SiO2 supported catalyst on the basis of the catalyst weight. The slight decrease of the H2 formation rate at the initial stage of the reaction may be attributed to the oxidation of the catalyst by water. The formation rate of hydrogen was about three times larger than that of CO2 over both

Table 1 Activity and selectivity of various supported Pt, Ru and PtRu catalysts Catalysts Formation rate (mmol h1 g1) H2 5 wt.%Pt/SiO2 5 wt.%Ru/SiO2 5 wt.%PtRu/SiO2 5 wt.%PtRu/Al2O3 5 wt.%PtRu/MgO 5 wt.%PtRu/ZrO2 5 wt.%PtRu/CeO2 5 wt.%PtRu/TiO2 7.0 58.2 123.2 68.2 93.6 133.0 74.0 205.8 CO 0.4 55.2 10.2 11.4 1.0 8.0 0.0 6.6 CO2 1.4 0.0 26.6 9.4 24.0 36.4 0.0 66.0 0.26 2.14 5.57 1.61 2.20 3.25 0.61 6.39 76.5 0.0 72.3 45.1 95.9 82.0 90.9 29.0 29.5 12.0 29.4 23.0 22.2 65.7 17.5 TOF (H2) (104 s1) CO2 selectivity D (%)

Pt:Ru = 1:1, loading of Pt: 5 wt.%.

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Table 2 Effect of reduction temperature on activity and selectivity of TiO2 supported Pt, Ru and PtRu catalysts (Pt:Ru = 1:1, loading of Pt: 5 wt.%) Catalysts Formation rate (mmol h1 g1) H2 PtRu/TiO2(473) PtRu/TiO2(673) PtRu/TiO2(723) Pt/TiO2(473) Pt/TiO2(673) Pt/TiO2(723) Pt/TiO2(723)a Ru/TiO2(673)
a

TOF (H2) (104 s1) CO2 29.8 66.0 106.8 16.8 27.6 34.3 2.5 4.7 6.4 10.6 5.2 6.5 5.3 1.5

CO2 selectivity

D (%) Scheme 1. Reaction scheme of liquid phase methanol reforming over supported PtRu catalysts.

CO 21.2 6.6 9.6 15.6 7.2 0.0 1.7

158.6 205.8 321.6 118.2 112.4 105.7 12.1

58.4 90.9 91.8 51.8 79.2 >99 29.9

18.5 17.5 16.5 24.9 18.9 21.8 15.2 9.0

Fresh catalyst (after reduction by hydrogen at 723 K).

hand, Ru/TiO2 catalyst exhibited low activity and selectivity (29.9%) for the reforming reaction. From these experimental results, it is concluded that the improvement of catalytic activities over PtRu/TiO2 catalysts by higher reduction temperature is not caused by the SMSI effect, but by more complete alloying of Pt and Ru metals by the reduction at higher temperatures. 3.3. Reaction scheme over PtRu/TiO2 catalyst Takezawa and coworkers reported that in the steam reforming, methanol is dehydrogenated to HCHO and HCOOCH3 followed by the oxidation with water over copper catalysts, while methanol is decomposed to CO and H2 through the decomposition of HCHO [1,10]. As mentioned above, we have already reported the reaction scheme of liquid phase reforming of methanol over PtRu/SiO2 catalyst [8]. From our study, in the methanol reforming reaction, PtRu/SiO2 catalyst exhibited much higher activity than Pt/SiO2 and Ru/SiO2 catalysts. The reforming reaction over PtRu/SiO2 catalyst proceeded through HCOOCH3 and HCOOH and the CO2 formation did not proceed via HCHO decomposition. Scheme 1 shows a schematic representation of the reaction pathways we have proposed in the formation of H2 in the methanol reforming reaction over the PtRu/SiO2 catalyst, where dehydrogenation of methanol is the rate determining step. In this study, we investigated a reaction scheme over TiO2 supported PtRu catalyst by the kinetic reaction measurements. Table 3 summarizes the rate of formation of H2, CO2 and CO, combined with the data over the silica supported PtRu catalyst. TiO2 supported catalyst exhibited higher selectivity to CO2 during both reforming of methanol and HCHO than those over SiO2 supported PtRu catalyst. From the results indicated in the table, it is clear that the ratios of H2 formation from each
Table 3 Catalytic activity for various reforming reactions over TiO2 or SiO2 supported PtRu catalysts Reactant Support Rate of formation (mmol h1 g1) H2 CH3OHH2O HCHOH2O HCOOCH3H2O HCOOHH2O TiO2 SiO2 TiO2 SiO2 TiO2 SiO2 TiO2 SiO2 211.2 123.2 777.6 618.4 654.0 453.2 934.8 721.2 CO 8.4 10.2 1008.0 794.0 235.2 145.6 1038.0 0.0 CO2 61.2 26.6 147.6 32.8 806.4 527.4 1215.6 863.0 87.9 72.4 12.8 4.0 77.4 78.4 53.9 100.0 CO2 selectivity (%)

of interaction between Pt and TiO2 will be described in the following section. 3.2. Effect of prereduction temperature of PtRu/TiO2 catalysts on their activity for the reforming reactions Table 2 summarizes the changes in the catalytic activities of PtRu/TiO2 in liquid phase methanol reforming with the temperature of reduction by hydrogen. The formation rate of hydrogen and CO2 increased drastically with the increase of reduction temperature. The H2 formation rate over PtRu/TiO2 reduced at 723 K (HTR) was about twice larger than that over the catalyst reduced at 473 K (LTR). On the contrary, the formation rate of CO decreased with the increase of reduction temperatures and the selectivity to CO2 reached 91.8% over the HTR catalyst. Metal dispersion determined by H2 chemisorption slightly decreased with the increase of reduction temperatures indicating the occurrence of the strong metal support interaction (SMSI) in the HTR catalyst. It is well known that SMSI effect occurs when titania-supported platinum group metals were reduced above 700 K [13]. Tauster and Fang reported that after H2 reduction of 2 wt.%Pt/TiO2 at 773 K, dispersion of Pt determined by H2 adsorption reduced from 88% to nearly 0%. From their other report, the decrease of the amount of H2 chemisorption began above 473 K of hydrogen treatment. The H/Pt value after reduction at 473 K was 0.35 and 0.06 at 673 K and 0.02 at 773 K [14]. To clarify the effect of the interaction between metal and TiO2 support, the catalytic activities over the single component catalysts, e.g. Pt/TiO2 and Ru/TiO2 were examined. As shown in the bottom columns in Table 2, the rate of hydrogen formation decreased accompanied with the increase of reduction temperatures. Because TOF was not changed by the reduction temperature over Pt/TiO2 catalysts, the decrease of the H2 formation rate may be attributed to the decrease of dispersion caused by the metal support interaction. The selectivity to CO2 was drastically improved by the increase of the reduction temperature and reached 99% over Pt/TiO2 reduced at 723 K. It is suggested that the interaction of Pt with the partially reduced TiO2 is responsible for the improvement of the selectivity over TiO2 supported catalysts. On the other

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Fig. 2. TEM images of various supported PtRu catalysts after liquid phase reforming of methanol with water (a) PtRu/SiO2, (b) PtRu/MgO, (c) PtRu/Al2O3 and (d) PtRu/TiO2.

reaction over PtRu/TiO2 catalyst are almost same with the ratio over PtRu/SiO2 catalyst, suggesting the similarity of the reaction scheme between these two kinds of supported PtRu catalyst. Therefore, we concluded that the reforming reaction over PtRu/TiO2 did not proceed through HCHO intermediate but through the intermediates of partly dehydrogenated HCOOCH3 species. 3.4. Morphology of supported PtRu catalyst Fig. 2 shows the TEM images of various supported PtRu catalysts after the reforming reaction of methanol. On the Pt Ru/SiO2 catalyst, a bimodal distribution of spherical crystal particles was observed with the range of particle diameter

between 5 and 2 nm. Both Pt and Ru elements were detected in these particles by energy dispersive X-ray spectroscopy (EDS) analyses. On the other hand, over PtRu/MgO and Pt Ru/Al2O3 catalysts, highly dispersed nano-crystallites with a uniform particle sizes were observed. On the TiO2 supported catalyst, the observed metal particles were smaller than those over SiO2 supported catalysts. An average size of the metal particles on TiO2 was 2.4 nm. The metal particle on TiO2 seems to adhere strongly to the substrate because their shapes were hemisphere having a larger contact area with TiO2, while the shapes of metal particles on SiO2 or Al2O3 were spherical. In addition, these particles seem to be covered with the several overlayers of the TiOx oxide. The magnied image of the PtRu/TiO2(HTR) catalyst and a further magnied

Fig. 3. TEM images of TiO2 supported PtRu catalysts reduced at 723 K after reaction (inset: high magnication image of supported metal particle).

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image of the metal particle supported on TiO2 are shown in Fig. 3. The crystal lattice distance observed in the metal particles supported on TiO2 is almost identical to the reported value of 0.38 nm for PtRu alloy [11], indicating that these particles are the PtRu alloy. Datye et al. studied structure change of supported Pt on the atomic scale by using HRTEM technique and reported that the stable monolayer of suboxide of Ti formed on (1 1 1) surfaces of Pt [12]. They suggested that the monolayer is composed of Ti atoms that are bonded to Pt atoms on the (1 1 1) surface and a part of Pt atom has a bonding with Ti atoms and Pt3Ti was constructed in some extent. In their report, Pt particles on TiO2 surface are wellfaced cuboctahedral shapes, whereas on Al2O3 and amorphous SiO2 the Pt particles are more spherical. Fig. 4 shows the TEM images of the fresh PtRu/TiO2 catalysts after H2 reduction at 723 K, where the oxide overlayers look thicker than those observed on the catalysts after reforming reaction (Fig. 3). As shown in the bottom column of Table 2, the dispersion of Pt/TiO2(723) before reforming reaction showed a small value (15.2%). The diameter of the metal particles estimated from the amount of hydrogen adsorption (7.5 nm) was signicantly larger than that determined by TEM (2.4 nm). It is suggested that the adsorption of hydrogen was inhibited by covering the metal surface with oxide layers, which was observed by TEM. The drastic change of the amount of H2 chemisorption before and after liquid phase reforming reaction indicates that the SMSI state is not stable in the reforming condition because the catalyst is suspended in a boiling methanol aqueous solution. 3.5. Chemical states of supported PtRu catalysts The XPS measurements were applied to investigate the chemical states of surface species on the PtRu/TiO2 catalysts.

Fig. 5 shows the Pt 4f, Ru 3d, and Ti 2p spectra of PtRu/ TiO2 catalysts after H2 treatment (b.r.) and after reforming reaction (a.r.). The peak positions and shape of these spectra were not changed before and after the reforming reaction. The Pt 4f spectrum of PtRu/TiO2 catalyst reveals a presence of slightly oxidized state of Pt species because the peak position observed at 71.4 eV is shifting from its zerovalent value of 71.1 eV [15]. In addition, the existence of oxidized state of platinum is suggested because the ratio of the height to Pt 4f5/2 peak of Pt 4f7/2 peak shows higher value than the reported value of the pure metal of Pt (Pt 4f5/2:Pt 4f7/2 = 0.85:1.00). Signicant shift of Ru 3d spectra observed at 280.5 eV from its zerovalent value (280.0 eV [15]) suggests that Ru species exists as RuO2. On the other hand, the binding energy of Ti 2p peak was smaller by 0.6 eV than that of pure TiO2. Accordingly, the surface of Ti oxide was reduced partially during hydrogen pretreatment. Otomo et al. reported an electro-catalytic activity of Pt/ TiO2, Pt/C, and PtRu/C for the anodic methanol oxidation [9]. In their study, from XPS measurements, binding energy of Pt 4f peak of Pt/TiO2 is larger than that of Pt/C. They explained that the interaction between positively charged Pt on TiO2 and adsorbed CO was weaker than that over Pt/C, and thus poisoning of Pt catalysts is suppressed. Similar positive shift in XPS spectra are observed in various Pt alloys, which have an excellent CO tolerance [16]. In our study, the positive shifts observed in the Pt 4f transition may be caused by both alloying of PtRu and the interaction with TiO2. The interaction of Pt with TiO2 and alloying with Ru may have a similar effect for the improvement of the catalytic activity and selectivity for CO2 in the liquid phase reforming of methanol.

Fig. 4. TEM images of TiO2 supported PtRu catalysts after reduction at 723 K (insets: high magnication image of supported metal particle).

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Fig. 5. X-ray photoelectron spectra of PtRu/TiO2 catalysts (a)(c): after H2 reduction, (d)(f): after reforming reaction.

4. Conclusions In the liquid phase methanol reforming with water, PtRu/ TiO2 catalyst exhibited highest activity in our investigation. Basic oxide support improved the selectivity to CO2 and acidic support suppressed both catalytic activity and selectivity. The interaction of Pt with the partially reduced TiO2 is responsible for the improvement of selectivity over TiO2 supported catalysts. Higher temperature reduction of PtRu/TiO2 improved their catalytic activity and selectivity by complete alloying of Pt and Ru. The reforming reaction over PtRu/TiO2 catalyst proceeded through partially dehydrogenated methylformate and formate intermediates with a similar mechanism as that over SiO2 supported PtRu catalyst. Acknowledgement This work was nancially supported by High-Tech Research Center Project from the Ministry of Education Science, Sports and Culture. References
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