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DFT study of nickel-catalyzed low-temperature methanol synthesis


McGuinness, DS and Patel, J and Amin, MH and Bhargava, SK, DFT study of nickel-catalyzed low-temperature methanol synthesis, ChemCatChem, 9, (10) pp. 1837-1844. ISSN 1867-3880 (2017) [Refereed Article]

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Copyright 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

DOI: doi:10.1002/cctc.201700213


Low-temperature methanol synthesis (CO+2H2→CH3OH) catalyzed by a homogeneous nickel/alkali metal alkoxide system has been studied theoretically. Two broad mechanistic possibilities, the direct hydrogenation of CO by nickel formyl species and indirect hydrogenation via methyl formate formation, have been examined. The most favorable mechanism involves the methanolysis of CO to methyl formate catalyzed by an ether complex of sodium methoxide followed by the stepwise hydrogenation of methyl formate to formaldehyde and then to a nickel methoxide, in which both steps are mediated by a nickel hydride. In the final step the nickel methoxide is hydrogenated to release methanol. The conversion of methyl formate to the nickel methoxide is predicted to be rate limiting, and the nickel hydride is the most likely catalyst resting state. The theoretical results are discussed in the context of existing experimental observations, and a good agreement with past studies was obtained.

Item Details

Item Type:Refereed Article
Keywords:low-temperature methanol synthesis, nickel, alkali, metal alkoxide
Research Division:Chemical Sciences
Research Group:Inorganic chemistry
Research Field:Organometallic chemistry
Objective Division:Energy
Objective Group:Energy transformation
Objective Field:Transformation of gas into fuels
UTAS Author:McGuinness, DS (Dr David McGuinness)
ID Code:124755
Year Published:2017
Funding Support:Australian Research Council (FT100100609)
Web of Science® Times Cited:3
Deposited By:Chemistry
Deposited On:2018-03-07
Last Modified:2018-04-10

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