Journal
ENERGY & ENVIRONMENTAL SCIENCE
Volume 5, Issue 7, Pages 7762-7770Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c2ee21519e
Keywords
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Funding
- DOE/LBNL Grant [403801]
- Helios Solar Energy Research Center (SERC) [51HE112B]
- Office of Science, Office of Basic Energy Sciences, Department of Energy [DE-AC02-05CH11231]
- NSF grant [CHE-1111900]
- National Science Foundation
- Miller Institute for Basic Research
- Direct For Mathematical & Physical Scien [1111900] Funding Source: National Science Foundation
- Division Of Chemistry [1111900] Funding Source: National Science Foundation
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We recently reported the catalytic generation of hydrogen from water mediated through the in situ reduction of the molybdenum(IV)-oxo complex [(PY5Me(2))MoO](2+) (1; PY5Me(2) = 2,6-bis(1,1-bis(2-pyridyl)ethyl)pyridine) at a mercury electrode. To gain further insight into this unique molecular motif for hydrogen production, we have now examined the competence of this complex for the catalytic reduction of protons on an alternative electrode material. Herein, we demonstrate the ability of the molybdenum-oxo complex 1 to reduce protons at a glassy carbon electrode in acidic organic media, where the active catalyst is shown to be diffusing freely in solution. Cyclic and rotating disk voltammetry experiments reveal that three reductive electrochemical processes precede the catalytic generation of hydrogen, which occurs at potentials more negative than -1.25 V vs. SHE. Gas chromatographic analysis of the bulk electrolysis cell headspace confirms that hydrogen is generated at a Faradaic efficiency of 99%. Under pseudo-first order conditions with an acid-to-catalyst ratio of >290, a rate constant of 385 s(-1) is calculated for the reduction of acetic acid in acetonitrile. Taken together, these data show that metal-oxo complex 1 is a competent molecular motif for catalytic generation of hydrogen from protons under soluble and diffusion-limited conditions.
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