Infrared study of methyl formate and formaldehyde adsorption on reduced and oxidised silica-supported copper catalysts

Millar, Graeme J., Rochester, Colin H., & Waugh, Kenneth C. (1991) Infrared study of methyl formate and formaldehyde adsorption on reduced and oxidised silica-supported copper catalysts. Journal of the Chemical Society, Faraday Transactions, 87(17), pp. 2785-2793.

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Infrared spectra are reported of methyl formate and formaldehyde adsorbed at 300 K on silica, Cu/SiO2 reduced in hydrogen and Cu/SiO2 which had been oxidised by exposure to nitrous oxide after reduction. Silanol groups on silica form hydrogen bonds with carbonyl groups in weakly adsorbed methyl formate molecules. Methyl formate ligates via its carbonyl groups to Cu atoms in the surface of reduced copper. A low residual concentration of surface oxygen on copper promoted the slow reaction of ligated methyl formate to give a bridging formate species on copper and adsorbed methoxy groups. Methyl formate did not ligate to an oxidised copper surface but was rapidly chemisorbed to give unidentate formate and methoxy species. Formaldehyde slowly polymerises on silica to form trioxane and other oxymethylene species. The reaction is faster over Cu/SiO2 which, in the reduced state, also catalyses the formation of bridging formate anions adsorbed on copper. The reaction between formaldehyde and oxidised Cu/SiO2 leads to both unidentate and bidentate formate and adsorbed water.

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ID Code: 61969
Item Type: Journal Article
Refereed: Yes
Keywords: infrared, catalyst, formaldehyde, methyl formate, copper
DOI: 10.1039/FT9918702785
ISSN: 0368-1769
Subjects: Australian and New Zealand Standard Research Classification > CHEMICAL SCIENCE (030000) > PHYSICAL CHEMISTRY (INCL. STRUCTURAL) (030600) > Catalysis and Mechanisms of Reactions (030601)
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Copyright Owner: Copyright 1991 Royal Society of Chemistry
Copyright Statement: Restrictions on further re-use and further distribution
Deposited On: 21 Aug 2013 22:56
Last Modified: 21 Aug 2013 22:57

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