The water gas shift reaction catalyzed by Rh6(CO)16 adsorbed on alumina or [Rh(CO)2Cl]2 adsorbed on alumina, Na-Y zeolite and H-Y zeolite

Jean-Marie Maurice Basset*, A. Theolier, D. Commereuc, Y. Chauvin

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

46 Scopus citations

Abstract

Rh6(CO)16 chemisorbed on η-alumina or [Rh(CO)2Cl]2 chemisorbed on η-alumina, Na-Y zeolite and H-Y zeolite catalyze the water gas shift reaction to various degrees. The following order of activity was observed: alumina > Na-Y > H-Y zeolite. With alumina the reaction occurs between 25 and 100°C. Turnover numbers as high as 255/Rh atom/h are obtained at 50°C and under 50 atm. These turnover numbers are the same whether the precursor complex is Rh6(CO)16 or [Rh(CO)2Cl]2. The mechanism of such a reaction has been deduced from infrared studies, mass balance and labeling experiments. It involves three steps: electrophilic attack by surface protons on the metallic frame with formation of RhI(CO)2(OAl{A figure is presented})(HOAl{A figure is presented}) and possibly RhIII(H)(H)(OAl{A figure is presented})HOAl{A figure is presented}); reductive elimination of H2 from Rh(H)(H)(OAl{A figure is presented})(HOAl{A figure is presented}) under CO pressure; and nucleophilic attack by water on CO coordinated to rhodium(I) with formation of CO2, H+ and regeneration of Rh6(CO)16. If the CO pressure is too low or if liquid water is used, aging of the catalyst occurs which seems to be due to the formation of metallic rhodium. The intermediacy of [Rh(CO)4]- is also suspected in the step of metal-metal bond formation.

Original languageEnglish (US)
Pages (from-to)147-158
Number of pages12
JournalJournal of Organometallic Chemistry
Volume279
Issue number1-2
DOIs
StatePublished - Jan 8 1985

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Fingerprint

Dive into the research topics of 'The water gas shift reaction catalyzed by Rh<sub>6</sub>(CO)<sub>16</sub> adsorbed on alumina or [Rh(CO)<sub>2</sub>Cl]<sub>2</sub> adsorbed on alumina, Na-Y zeolite and H-Y zeolite'. Together they form a unique fingerprint.

Cite this