Bifunctional organorhodium solid acid catalysts for methanol carbonylation

Lee D. Dingwall, Adam F. Lee, Jason M. Lynam, Karen Wilson, Luca Olivi, Jon M.S. Deeley, Sander Gaemers, Glenn J. Sunley

Research output: Contribution to journalArticlepeer-review


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.
Original languageEnglish
Pages (from-to)1368-1376
Number of pages9
JournalACS Catalysis
Issue number7
Early online date17 May 2012
Publication statusPublished - 6 Jul 2012


  • rhodium
  • carbonylation
  • methanol
  • heteropoly acid


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