Applied Catalysis A: General 299 (2006) 285–291 www.elsevier.

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Remarkable support effect for liquid phase methanol reforming with water over supported Pt–Ru 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 Pt–Ru 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 Pt–Ru/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 Pt–Ru alloy, respectively. The reforming reaction over Pt–Ru/TiO2 catalyst proceeded through partially dehydrogenated HCOOCH3 and HCOOH intermediate with the similar mechanism as that over SiO2 supported Pt–Ru catalyst. # 2005 Elsevier B.V. All rights reserved.
Keywords: Liquid phase reforming of methanol; Hydrogen production; Support effect; Pt–Ru/TiO2 catalyst

1. Introduction The development of efficient 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 insufficient 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 significant 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

After reduction in hydrogen at 473 K the sample was transformed to the analysis chamber without exposure to air. Samples were prepared by molding in a thin disk shape and introduced into a pretreatment chamber. 60 cm3 of degassed methanol solution (typically 10% CH3OH/H2O) was introduced into the reactor under nitrogen atmosphere by using Schlenk technique. After the pretreatment of catalyst. The reaction experiments were performed usually between 350 and 357 K. SiO2 (Japan Aerosil. VOx.2. the loading of Pt was adjusted to 5 wt. The simplest method of promotion of the catalytic activity is the use of alloying of Pt with different metals.e. Al2O3 (AL2O3. The other method for promotion is a combination of Pt with a base metal oxide. Lasch et al. Although DMFC studies described above have been investigated by the half cell experiments at acidic conditions. Aerosil300). Gas phase products were analyzed by TCD gas chromatograph (GC-8A. MoOx and VOx to Pt–Ru electrode [19]. since water adsorbed on the tungsten trioxide [18]. . 2. Shimadzu).22] were reported to promote catalytic activities of Pt or Pt–Ru anode catalyst for the anodic oxidation of methanol. Beckmann Coulter) at 298 K. 40 kPa for 5 h. MgO (Wako Pure Chemical). 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 reaction mechanisms over TiO2 supported Pt–Ru catalyst was also investigated by a kinetic approach. Otomo et al. 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. Experimental 2. Before measurement. such as CO. Pt–Sn. JEOL) with an acceleration voltage of 200 kV and LaB6 cathode was applied for high resolution images of the supported catalysts. the interaction between Pt and CO is weaker on TiO2 than on conventional carbon supported Pt anode [9]. 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 reflux condenser connected to a closed gas circulation system.17]. 2. 2. Preparation of catalysts Supported Pt–Ru catalysts were prepared by conventional impregnation method. 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. the used catalysts were dried at room temperature and reduced at 473 K for 3 h in a flow of hydrogen at atmospheric pressure. MoOx [19] and TiO2 [9. investigated electro-catalytic activity of Pt/TiO2 catalyst for the anodic methanol oxidation. Japan Aerosil). TiO2 (P-25. / Applied Catalysis A: General 299 (2006) 285–291 methanol. The adsorption amount of hydrogen or CO over used catalysts was measured by a static volumetric adsorption apparatus (Omnisorp100CX. reported the improvement of the catalytic activity towards methanol oxidation by the addition of WOx. Shimadzu) and liquid phase products were analyzed by FID gas chromatograph (GC-14B. 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 film. i. 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). But Pt itself is not sufficiently active to be useful commercially. especially the groups IV–VI transition metal oxides. Japan Aerosil).1.% and the molar ratio of Pt/Ru was unity. TOSOH) and CeO2 (Anan Kasei. we have investigated liquid phase reforming reaction of methanol over Pt–Ru metals supported on various oxides and the effect of support materials for catalytic activity and selectivity was discussed in depth.5 g of catalyst was placed in the reactor and then reduced under hydrogen flow atmosphere at 673 K. For all of the supported Pt–Ru catalysts. etc. J-3) were used for support materials. The dispersion (D (%).3. and the dehydrogenation of methanol is the rate determining step of the reaction. In our study on the methanol reforming reaction. Pt–Ru/SiO2 catalyst exhibited much higher activity than Pt/SiO2 and Ru/SiO2 catalysts. Pt–Os. The catalyst was then evacuated at 298 K for 1 h and a second adsorption isotherm was measured. Pt–Ir. These oxides used as a support were impregnated to an aqueous solution of H2PtCl6Á6H2O (Wako Pure Chemical) and RuCl3ÁnH2O (Wako Pure Chemical) followed by evaporation at 308 K and dried at 383 K for overnight.20]. 10 mA) was applied for chemical states of supported catalysts. The reforming reaction over Pt–Ru/SiO2 catalyst proceeded through HCOOCH3 and HCOOH. It is widely accepted that Pt–Ru alloy is the most active catalyst for the activation of methanol. Miyao et al. A X-ray photoelectron spectrometer (JPS9010. 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 reflux of the methanol solution started under vapor pressure and balanced nitrogen gas as a internal standard. The main purpose of our study is the development of more simple and compact system for production of pure hydrogen [8. [3]. Pt–Ru.286 T. A first adsorption isotherm was achieved so as to measure the total amount of adsorbed gases. JEOL) with Mg Ka X-ray source (10 kV. Among them. In the present study. 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. The 0. ZrO2 (PX-81.21. WOx [18. Characterization of catalysts A transmission electron microscope (JEM2010. From their reports.

5 12. 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.9 82.%Pt–Ru/ZrO2 5 wt.4 0.6 9.7 17.%. hydrogen was linearly produced for a longer reaction period whose amount reached to 800 mmol after 300 min. It is worth noticing that Pt–Ru catalysts supported on basic supports such as MgO.2 93. Hamnett et al. Time courses of liquid phase reforming of methanol with water at 350 K over TiO2 or SiO2 supported Pt–Ru catalyst.%Pt–Ru/MgO 5 wt. They claimed the formation of Pt–Ti oxide complex and explained the improvement of the electro-oxidation rate of methanol by the oxidation of Pt–CHO or Pt3HBBCOH residues to CO2.0 74. On the basis of turnover frequency determined by the amount of H2 chemisorption.2 65.0 0. investigated addition effect of WOx.0 29.9%) than the other catalysts.0 58. Over acidic supports.20 3. and it is suggested that the activation of water molecules proceeds on TiO2 support.0 8. Pt–Ru/TiO2 exhibited much higher activity (6.%Pt–Ru/TiO2 7. which may be explained by the oxidation of partially reduced ceria.T. TiO2 and ZrO2 exhibited higher selectivity toward CO2 formation in the methanol reforming reaction.4 1.0 – 90.0 205. Machida et al. They reported that the Pt/Ln0.4 23.0 66.%Ru/SiO2 5 wt. 1 shows the time courses of products formation during liquid phase methanol reforming with water at 353 K over Pt–Ru/TiO2 and Pt–Ru/SiO2 where H2 and CO2 were the major products with a small amount of CO.0 22.26 2.4 55. The selectivity to CO2 was calculated according to the formula shown as follows. On the contrary. Pt–Ru/Al2O3.4 Â 10À4 sÀ1) and selectivity (90.57 1. Miyao et al.%Pt–Ru/Al2O3 5 wt.3 45.0 29. SCO2 = CO2/ (CO2 + CO) Â 100%. ZrOx and TiOx on the catalytic activity for methanol oxidation [21].0 36.2 123.1WO3 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].39 76.61 2. Methanol reforming reaction over various supported Pt–Ru catalysts Fig.6 CO2 1.0 0. Over Pt–Ru/CeO2 catalyst.5 0.2 10.1 95.2 11. 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. Ru and Pt–Ru catalysts Catalysts Formation rate (mmol hÀ1 gÀ1) H2 5 wt.9 29.0 6.5 TOF (H2) (Â10À4 sÀ1) CO2 selectivity D (%) Pt:Ru = 1:1. %).4 0.8 CO 0.4 24.0 26. The activity and selectivity were greatly affected by the kinds of support employed. 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.6 133.1. .%Pt–Ru/SiO2 5 wt. 3.0 72. 1.61 6.25 0. which oxidize the methanol intermediates adsorbed on Pt sites.2 68. Over TiO2 supported catalyst.1WO3. investigated addition of tungsten bronze (Ln0. Pt–Ru/MgO and Pt–Ru/ZrO2 catalysts exhibited lower TOF of hydrogen formation.%Pt–Ru/CeO2 5 wt. large amount of hydrogen was formed at the initial stage of the reaction accompanied with the significant decrease of the H2 formation rate. loading of Pt: 5 wt.14 5.%Pt/SiO2 5 wt. / Applied Catalysis A: General 299 (2006) 285–291 287 catalysts corresponding to the reaction stoichiometry described below: CH3 OH þ H2 O ¼ 3H2 þ CO2 : In Table 1. Results and discussion 3. The poor selectivity of Pt–Ru/Al2O3 suggested that acidic property has a negative effect for the CO2 formation. Similar process may take place on our catalysts. further dehydrogenation of partially dehydrogenated intermediates may take place to form CO. The importance Fig. Ln = rare earth) to Pt electrode for methanol oxidation. the catalytic activity and selectivity over various supported Pt–Ru catalysts were summarized with the values of metal dispersion (D.

The selectivity to CO2 was drastically improved by the increase of the reduction temperature and reached 99% over Pt/TiO2 reduced at 723 K.4 105.4 12.9 91.8 66.288 T.8 721. we have already reported the reaction scheme of liquid phase reforming of methanol over Pt–Ru/SiO2 catalyst [8].4 78. TiO2 supported catalyst exhibited higher selectivity to CO2 during both reforming of methanol and HCHO than those over SiO2 supported Pt–Ru catalyst.0 CO2 selectivity (%) of interaction between Pt and TiO2 will be described in the following section.9 72.0 77.0 – 1.6 34. Ru and Pt–Ru catalysts (Pt:Ru = 1:1. the decrease of the amount of H2 chemisorption began above 473 K of hydrogen treatment. 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. On the other .0 106.0 Fresh catalyst (after reduction by hydrogen at 723 K).06 at 673 K and 0.6 7.8 27. The H/Pt value after reduction at 473 K was 0.4 10. To clarify the effect of the interaction between metal and TiO2 support.6 32.2 1008. From these experimental results. The H2 formation rate over Pt–Ru/TiO2 reduced at 723 K (HTR) was about twice larger than that over the catalyst reduced at 473 K (LTR).6 15.2 6.4 53.2 9. Pt–Ru/SiO2 catalyst exhibited much higher activity than Pt/SiO2 and Ru/SiO2 catalysts. it is concluded that the improvement of catalytic activities over Pt–Ru/TiO2 catalysts by higher reduction temperature is not caused by the SMSI effect.6 9. Ru/TiO2 catalyst exhibited low activity and selectivity (29.9%) for the reforming reaction.7 158. hand. 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 Pt–Ru/SiO2 catalyst.8 321.9 100.8 806.0 235.5 4. / Applied Catalysis A: General 299 (2006) 285–291 Table 2 Effect of reduction temperature on activity and selectivity of TiO2 supported Pt. The reforming reaction over Pt–Ru/SiO2 catalyst proceeded through HCOOCH3 and HCOOH and the CO2 formation did not proceed via HCHO decomposition.9 18.4 1215. it is clear that the ratios of H2 formation from each Table 3 Catalytic activity for various reforming reactions over TiO2 or SiO2 supported Pt–Ru catalysts Reactant Support Rate of formation (mmol hÀ1 gÀ1) H2 CH3OH–H2O HCHO–H2O HCOOCH3–H2O HCOOH–H2O TiO2 SiO2 TiO2 SiO2 TiO2 SiO2 TiO2 SiO2 211.3 – 1.8 51. It is well known that SMSI effect occurs when titania-supported platinum group metals were reduced above 700 K [13].5 CO2 selectivity D (%) Scheme 1. Reaction scheme of liquid phase methanol reforming over supported Pt–Ru catalysts.02 at 773 K [14]. In this study. Reaction scheme over Pt–Ru/TiO2 catalyst Takezawa and coworkers reported that in the steam reforming.6 147.5 16.2 >99 – 29.4 654.9 21. On the contrary. loading of Pt: 5 wt.7 6.%) Catalysts Formation rate (mmol hÀ1 gÀ1) H2 Pt–Ru/TiO2(473) Pt–Ru/TiO2(673) Pt–Ru/TiO2(723) Pt/TiO2(473) Pt/TiO2(673) Pt/TiO2(723) Pt/TiO2(723)a Ru/TiO2(673) a TOF (H2) (Â10À4 sÀ1) CO2 29. CO 21. From the results indicated in the table.6 118.8 79. the catalytic activities over the single component catalysts.8% over the HTR catalyst.4 527.8 16. The formation rate of hydrogen and CO2 increased drastically with the increase of reduction temperature.2 145. Tauster and Fang reported that after H2 reduction of 2 wt.0 453.0 CO2 61.4 90. Pt/TiO2 and Ru/TiO2 were examined.2 934. From our study.6 863.g. the rate of hydrogen formation decreased accompanied with the increase of reduction temperatures.2 CO 8.4 10.2 123. dispersion of Pt determined by H2 adsorption reduced from 88% to nearly 0%.2 112.7 – 12.6 618.6 1038. while methanol is decomposed to CO and H2 through the decomposition of HCHO [1. 3. in the methanol reforming reaction.0 0.5 24.8 15.5 17.35 and 0. As mentioned above.%Pt/TiO2 at 773 K. Effect of prereduction temperature of Pt–Ru/TiO2 catalysts on their activity for the reforming reactions Table 2 summarizes the changes in the catalytic activities of Pt–Ru/TiO2 in liquid phase methanol reforming with the temperature of reduction by hydrogen.1 58. Miyao et al. 3.0 87.2 26.0 794.2. but by more complete alloying of Pt and Ru metals by the reduction at higher temperatures. Because TOF was not changed by the reduction temperature over Pt/TiO2 catalysts. 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.9 18. we investigated a reaction scheme over TiO2 supported Pt–Ru catalyst by the kinetic reaction measurements. From their other report.6 5.6 205. the formation rate of CO decreased with the increase of reduction temperatures and the selectivity to CO2 reached 91.8 4. where dehydrogenation of methanol is the rate determining step. e. combined with the data over the silica supported Pt–Ru catalyst.10]. As shown in the bottom columns in Table 2. Table 3 summarizes the rate of formation of H2. CO2 and CO.2 6. methanol is dehydrogenated to HCHO and HCOOCH3 followed by the oxidation with water over copper catalysts.2 0.3.2 777.3 – 2. the decrease of the H2 formation rate may be attributed to the decrease of dispersion caused by the metal support interaction.5 5.

TEM images of TiO2 supported Pt–Ru catalysts reduced at 723 K after reaction (inset: high magnification image of supported metal particle). we concluded that the reforming reaction over Pt–Ru/TiO2 did not proceed through HCHO intermediate but through the intermediates of partly dehydrogenated HCOOCH3 species. Miyao et al. (c) Pt–Ru/Al2O3 and (d) Pt–Ru/TiO2. In addition. a bimodal distribution of spherical crystal particles was observed with the range of particle diameter between 5 and 2 nm. 3. On the TiO2 supported catalyst. The magnified image of the Pt–Ru/TiO2(HTR) catalyst and a further magnified Fig. 3. (b) Pt–Ru/MgO. 2 shows the TEM images of various supported Pt–Ru catalysts after the reforming reaction of methanol. these particles seem to be covered with the several overlayers of the TiOx oxide. the observed metal particles were smaller than those over SiO2 supported catalysts. Both Pt and Ru elements were detected in these particles by energy dispersive X-ray spectroscopy (EDS) analyses. An average size of the metal particles on TiO2 was 2. The metal particle on TiO2 seems to adhere strongly to the substrate because their shapes were hemisphere having a larger contact area with TiO2. Morphology of supported Pt–Ru catalyst Fig.T. . / Applied Catalysis A: General 299 (2006) 285–291 289 Fig. On the other hand. over Pt–Ru/MgO and Pt– Ru/Al2O3 catalysts. On the Pt– Ru/SiO2 catalyst. while the shapes of metal particles on SiO2 or Al2O3 were spherical. suggesting the similarity of the reaction scheme between these two kinds of supported Pt–Ru catalyst.4. reaction over Pt–Ru/TiO2 catalyst are almost same with the ratio over Pt–Ru/SiO2 catalyst. highly dispersed nano-crystallites with a uniform particle sizes were observed. Therefore. 2. TEM images of various supported Pt–Ru catalysts after liquid phase reforming of methanol with water (a) Pt–Ru/SiO2.4 nm.

3. where the oxide overlayers look thicker than those observed on the catalysts after reforming reaction (Fig. Fig.) and after reforming reaction (a. 3).290 T.6 eV than that of pure TiO2. the dispersion of Pt/TiO2(723) before reforming reaction showed a small value (15. Fig. The diameter of the metal particles estimated from the amount of hydrogen adsorption (7. the binding energy of Ti 2p peak was smaller by 0. 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. In their report. the surface of Ti oxide was reduced partially during hydrogen pretreatment. 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. Significant shift of Ru 3d spectra observed at 280. and thus poisoning of Pt catalysts is suppressed. Datye et al. Miyao et al. and Pt–Ru/C for the anodic methanol oxidation [9]. It is suggested that the adsorption of hydrogen was inhibited by covering the metal surface with oxide layers.r. On the other hand.5 nm) was significantly larger than that determined by TEM (2.r. Ru 3d. 5 shows the Pt 4f. Pt particles on TiO2 surface are wellfaced cuboctahedral shapes. In addition.85:1.1 eV [15].5.00). 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. The peak positions and shape of these spectra were not changed before and after the reforming reaction. Accordingly.4 nm). In their study. They explained that the interaction between positively charged Pt on TiO2 and adsorbed CO was weaker than that over Pt/C. binding energy of Pt 4f peak of Pt/TiO2 is larger than that of Pt/C.5 eV from its zerovalent value (280.0 eV [15]) suggests that Ru species exists as RuO2. The Pt 4f spectrum of Pt–Ru/TiO2 catalyst reveals a presence of slightly oxidized state of Pt species because the peak position observed at 71. the positive shifts observed in the Pt 4f transition may be caused by both alloying of Pt–Ru and the interaction with TiO2. As shown in the bottom column of Table 2. indicating that these particles are the Pt–Ru alloy.38 nm for Pt–Ru alloy [11]. Similar positive shift in XPS spectra are observed in various Pt alloys.2%). which have an excellent CO tolerance [16]. from XPS measurements. TEM images of TiO2 supported Pt–Ru catalysts after reduction at 723 K (insets: high magnification image of supported metal particle). whereas on Al2O3 and amorphous SiO2 the Pt particles are more spherical. which was observed by TEM. Pt/C. 4. 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. 4 shows the TEM images of the fresh Pt–Ru/TiO2 catalysts after H2 reduction at 723 K.4 eV is shifting from its zerovalent value of 71. Fig. and Ti 2p spectra of Pt–Ru/ TiO2 catalysts after H2 treatment (b. Otomo 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]. In our study. / Applied Catalysis A: General 299 (2006) 285–291 image of the metal particle supported on TiO2 are shown in Fig. The crystal lattice distance observed in the metal particles supported on TiO2 is almost identical to the reported value of 0. reported an electro-catalytic activity of Pt/ TiO2. . Chemical states of supported Pt–Ru catalysts The XPS measurements were applied to investigate the chemical states of surface species on the Pt–Ru/TiO2 catalysts. 3.).

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