Abstract
The adsorption and reactions of methanol have been investigated on Au metal supported by various oxides and carbon Norit of high surface area. Infrared spectroscopic studies revealed the dissociation of methanol at 300 K, which mainly occurs on the oxide-supports yielding methoxy species. The presence of Au already appeared in the increased amounts of desorbed products in the TPD spectra. The reaction pathway of the decomposition and the activity of the catalyst sensitively depend on the nature of the support. As regards the production of hydrogen the most effective catalyst is Au/CeO2 followed by Au/MgO, Au/TiO2 and Au/Norit. In contrast, on Au/Al2O3 the main process is the dehydration reaction yielding dimethyl ether. On Au/CeO2 the decomposition of methanol starts above ~500 K and approaches total conversion at 723–773 K. The products are H2 (~68%) and CO (~27%) with very small amounts of methane and CO2. The decomposition of methanol follows the first order kinetics. The activation energy of this process is 87.0 kJ/mol. The selectivity of H2 formation at 573–773 K was ~90%, this value increased to 97% using CH3OH:H2O (1:1) reacting mixture indicating the involvement of water in the reaction. No deactivation of Au catalysts was experienced at 773 K in ~10 h. It is assumed that the interface between Au and partially reduced ceria is responsible for the high activity of Au/CeO2 catalyst.
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Sandstede G, Veziroglu TN, Derive C, Pottier J (eds) (1972) Proceedings of the 9th world hydrogen energy conference, Paris, France, p 1745
Haryanto A, Fernando S, Murali N, Adhikari S (2005) Energy Fuels 19:2098
Muradov N (2001) Catal Commun 2:89
Marino F, Boveri M, Baronetti G, Laborde M (2001) Int J Hydrogen Energy 26:665
Galvita VV, Semin GL, Belyaev VD, Semikolenov VA, Tsiakaras P, Solyanin VA (2001) Appl Catal A Gen 220:123
Díagne C, Idriss H, Kiennemann A (2002) Catal Commun 3:565
Barthos R, Solymosi F (2007) J Catal 249:289
Koós Á, Barthos R, Solymosi F (2008) J Phys Chem C 112:2607
Barthos R, Széchenyi A, Solymosi F (2008) Catal Letts 120:161
Barthos R, Széchenyi A, Koós Á, Solymosi F (2007) Appl Catal A Gen 327:95
Solymosi F, Barthos R, Kecskeméti A (2008) Appl Catal A Gen 350:30
Haruta M, Kobayashi T, Sano H, Yamada N (1978) Chem Lett 2:405
Haruta M (1997) Catal Today 36:153
Bond GC, Thompson DT (1999) Catal Rev Sci Eng 41:319
Hutchings GJ (2002) Catal Today 72:11
Kung MC, Davis RJ, Kung HK (2007) J Phys Chem 111:11767
Chen MS, Goodman DW (2004) Science 306:252
Jannssens TVW, Carlsson A, Puig-Molina A, Clausen BS (2006) J Catal 240:108
Aguilar-Guerrero V, Gates BC (2008) J Catal 260:351
Ueda A, Haruta M (1999) Gold Bull 32:3
Solymosi F, Bánsági T, Süli Zakar T (2003) Phys Chem Chem Phys 5:4724
Mitov I, Klissurski D, Minchev C (2008) Comptes Rendus De L Acad Bulgare Des Sci 61:1003
Haruta M, Ueda A, Tsubota S, Torres Sanchez RM (1996) Catal Today 29:443
Nuhu A, Soares J, Gonzalez-Herrera M, Watts A, Hussein G, Bowker M (2007) Top Catal 44:293
Boccuzzi F, Chiorino A, Manzoli M (2003) J Power Sources 118:304
Manzoli M, Chiorino A, Boccuzzi F (2005) Appl Catal B Env 57:201
Busca G, Lamotte J, Lavalley JC, Lorenzelli V (1987) J Am Chem Soc 109:5197
Badri A, Binet C, Lavalley JC (1997) J Chem Soc Faraday Trans 93:1159
Finocchio E, Daturi M, Binet C, Lavalley JC, Blanchard G (1999) Catal Today 52:53
Boccuzzi F, Chiorino A, Manzoli M, Lu P, Akita T, Ichikawa S, Haruta M (2001) J Catal 202:256
Binet C, Daturi M (2001) Catal Today 70:155
Trovarelli A (ed) (2002) Catalysis by ceria and related materials. World scientific publishing company, Incorporated, USA
Bartheau MA, Madix RJ (1982) In: King DA, Woodruff DP (eds) The chemical physics of solid surface and heterogeneous catalysis. Elsevier, Amsterdam, p 95 (chapter 4)
Solymosi F, Berkó A, Tarnóczi TI (1984) Surf Sci 141:533
Hrbek J, De Paola R, Hoffmann FM (1986) Surf Sci 166:361
Davis JL, Barteau MA (1987) Surf Sci 187:387
Solymosi F, Berkó A, Tóth Z (1993) Surf Sci 285:197
Greeley J, Mavrikakis M (2004) J Am Chem Soc 126:3910
Lewis RJ, Zhicheng J, Winograd N (1989) J Am Chem Soc 111:4605
Guo X, Hanley L, Yates JT Jr (1989) J Am Chem Soc 111:3155
Solymosi F, Révész K (1991) J Am Chem Soc 113:9145
Rebholz M, Kruse N (1991) J Chem Phys 95:7745
Morkel M, Kaichev VV, Rupprechter G, Freund H-J, Prosvirin IP, Bukhtiyarov VI (2004) J Phys Chem B 108:12955
Lazaga MA, Wickham DT, Parker DH, Kastanas GN, Koel BE (1993) ACS Symp Ser 523:90
Gong J, Flaherty DW, Ojifinni RA, White JM, Mullins CB (2008) J Phys Chem C 112:5501
Solymosi F, Klivényi G (1993) J Electr Spectr 64/65:499
Raskó J, Solymosi F (1998) Catal Letts 54:40
Szabó ZG, Solymosi F (1961) Actes Congr Intern Catalyse 2e Paris 1960:1627
Solymosi F (1968) Catal Rev 1:233
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This work was supported by OTKA under contract number NI 69327. The authors express their thanks to P. Németh for TEM measurements.
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Gazsi, A., Bánsági, T. & Solymosi, F. Hydrogen Formation in the Reactions of Methanol on Supported Au Catalysts. Catal Lett 131, 33–41 (2009). https://doi.org/10.1007/s10562-009-0052-6
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DOI: https://doi.org/10.1007/s10562-009-0052-6