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

Aaron Appel, Daniel L DuBois, M. Rakowski DuBois

Research output: Contribution to journalArticle

139 Citations (Scopus)

Abstract

(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
Volume127
Issue number36
DOIs
Publication statusPublished - Sep 14 2005

Fingerprint

Molybdenum
Electrocatalysts
Sulfur
Dimers
Protons
Hydrogen
Atmosphere
Protonation
Ligands
Acetonitrile
Hydrides
Acids
Derivatives
Catalysts
Kinetics
acetonitrile
ferrocene

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Molybdenum-sulfur dimers as electrocatalysts for the production of hydrogen at low overpotentials. / Appel, Aaron; DuBois, Daniel L; Rakowski DuBois, M.

In: Journal of the American Chemical Society, Vol. 127, No. 36, 14.09.2005, p. 12717-12726.

Research output: Contribution to journalArticle

@article{c7c3b7e2b4694312b42d50e2cf2222c1,
title = "Molybdenum-sulfur dimers as electrocatalysts for the production of hydrogen at low overpotentials",
abstract = "(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.",
author = "Aaron Appel and DuBois, {Daniel L} and {Rakowski DuBois}, M.",
year = "2005",
month = "9",
day = "14",
doi = "10.1021/ja054034o",
language = "English",
volume = "127",
pages = "12717--12726",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "36",

}

TY - JOUR

T1 - Molybdenum-sulfur dimers as electrocatalysts for the production of hydrogen at low overpotentials

AU - Appel, Aaron

AU - DuBois, Daniel L

AU - Rakowski DuBois, M.

PY - 2005/9/14

Y1 - 2005/9/14

N2 - (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.

AB - (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.

UR - http://www.scopus.com/inward/record.url?scp=24744468030&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=24744468030&partnerID=8YFLogxK

U2 - 10.1021/ja054034o

DO - 10.1021/ja054034o

M3 - Article

VL - 127

SP - 12717

EP - 12726

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 36

ER -