Molybdenum-sulfur dimers as electrocatalysts for the production of hydrogen at low overpotentials

Aaron M. Appel, Daniel L. DuBois, M. Rakowski DuBois

Research output: Contribution to journalArticlepeer-review

159 Citations (Scopus)


(CpMoμ-S)2S2CH2, 2, and related derivatives serve as electrocatalysts for the reduction of protons with current efficiencies near 100%. The kinetics of the electrochemical reduction process has been studied, and the effects of varying the proton source, the solvent, the cyclopentadienyl substituents, and the sulfur substituents on the catalyst have been examined. The reduction of excess p-cyanoanilinium tetrafluoroborate under a hydrogen atmosphere in 0.3 M Et4NBF4/acetonitrile buffered at pH 7.6 is catalyzed by 2 at -0.64 V versus ferrocene, with an overpotential of 120 mV. Protonation of the sulfido ligand in 2 is an initial step in the catalytic process, and the rate-determining step at high acid concentrations appears to be the elimination of dihydrogen. The elimination may occur either from adjacent hydrosulfido sites or from a hydrosulfido-molybdenum hydride intermediate.

Original languageEnglish
Pages (from-to)12717-12726
Number of pages10
JournalJournal of the American Chemical Society
Issue number36
Publication statusPublished - Sep 14 2005

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Fingerprint Dive into the research topics of 'Molybdenum-sulfur dimers as electrocatalysts for the production of hydrogen at low overpotentials'. Together they form a unique fingerprint.

Cite this