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Surface Defects Activating New Reaction Paths: Formation of Formate during Methanol Oxidation on Ru(0001)
Author(s) -
Palacio Irene,
Rojo Juan M.,
Rodríguez de la Fuente Oscar
Publication year - 2012
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201200190
Subject(s) - formate , formaldehyde , methanol , catalysis , adsorption , chemistry , methyl formate , oxygen , reaction intermediate , inorganic chemistry , reaction mechanism , photochemistry , organic chemistry
Methanol was co‐adsorbed with oxygen on Ru(0001) under conditions approaching those of real catalysts: at room temperature and at relatively high pressures and exposures, together with a comparative analysis of flat and defective surfaces. To clarify reaction routes, parallel exposures to formaldehyde and oxygen have also been analyzed. It is found that for both mixtures of gases, a new reaction path is activated on defective surfaces, in which methanol is oxidized to formate. Furthermore, at variance with pure methanol adsorption, apart from CO, various intermediates are observed in both flat and defective surfaces. On flat surfaces, formaldehyde and formyl are recognized whereas on defective ones methoxy and formate are detected. A model involving steering effects is presented, which accounts for the activity of surface defects towards the synthesis of formate.