Characterization of precursors to methanol synthesis catalysts Cu/ZnO system

Millar, Graeme J., Holm, Ivan H., Uwins, Philippa J.R., & Drennan, John (1998) Characterization of precursors to methanol synthesis catalysts Cu/ZnO system. Journal of the Chemical Society, Faraday Transactions, 94(4), pp. 593-600.

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The composition of a series of hydroxycarbonate precursors to copper/zinc oxide methanol synthesis catalysts prepared under conditions reported as optimum for catalytic activity has been studied. Techniques employed included thermogravimetry (TG), temperature-programmed decomposition (TPD), X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), and Raman and FTIR spectroscopies. Evidence was obtained for various structural phases including hydrozincite, copper hydrozincite, aurichalcite, zincian malachite and malachite (the concentrations of which depended upon the exact Cu/Zn ratio used). Significantly, previously reported phases such as gerhardite and rosasite were not identified when catalysts were synthesized at optimum solution pH and temperature values, and after appropriate aging periods. Calcination of the hydroxycarbonate precursors resulted in the formation of catalysts containing an intimate mixture of copper and zinc oxides. Temperature-programmed reduction (TPR) revealed that a number of discrete copper oxide species were present in the catalyst, the precise concentrations of which were determined to be related to the structure of the catalyst precursor. Copper hydrozincite decomposed to give zinc oxide particles decorated by highly dispersed, small copper oxide species. Aurichalcite appeared to result ultimately in the most intimately mixed catalyst structure whereas zincian malachite decomposed to produce larger copper oxide and zinc oxide grains. The reason for the stabilization of small copper oxide and zinc oxide clusters by aurichalcite was investigated by using carefully selected calcination temperatures. It was concluded that the unique formation of an 'anion-modified' oxide resulting from the initial decomposition stage of aurichalcite was responsible for the 'binding' of copper species to zinc moieties.

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ID Code: 62041
Item Type: Journal Article
Refereed: Yes
Keywords: copper, catalyst, methanol, zinc oxide, characterization
DOI: 10.1039/A703954I
ISSN: 1364-5455
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 1998 Royal Society of Chemistry
Copyright Statement: Restrictions on further re-use and further distribution
Deposited On: 26 Aug 2013 00:36
Last Modified: 26 Aug 2013 00:36

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