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Bifunctional Organorhodium Solid Acid Catalysts for Methanol Carbonylation

Dingwall, L. D., Lee, Adam Fraser, Lynam, J. M., Wilson, Karen, Olivi, L., Deeley, J. M. S., Gaemers, S. and Sunley, G. J. 2012. Bifunctional Organorhodium Solid Acid Catalysts for Methanol Carbonylation. ACS Catalysis 2 (7) , pp. 1368-1376. 10.1021/cs3000528

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Robust, bifunctional catalysts comprising Rh(CO)(Xantphos) exchanged phosphotungstic acids of general formulas [Rh(CO)(Xantphos)]+n[H3–nPW12O40]n− have been synthesized over silica supports which exhibit tunable activity and selectivity toward direct vapor phase methanol carbonylation. The optimal Rh:acid ratio = 0.5, with higher rhodium concentrations increasing the selectivity to methyl acetate over dimethyl ether at the expense of lower acidity and poor activity. On-stream deactivation above 200 °C reflects Rh decomplexation and reduction to Rh metal, in conjunction with catalyst dehydration and loss of solid acidity because of undesired methyl acetate hydrolysis, but can be alleviated by water addition and lower temperature operation.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Cardiff Catalysis Institute (CCI)
Subjects: Q Science > QD Chemistry
Uncontrolled Keywords: rhodium; heteropoly acid; methanol; carbonylation; EXAFS
Publisher: ACS
ISSN: 2155-5435
Last Modified: 19 Mar 2016 23:10

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