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Title: Electrochemical Detection of Transient Cobalt Hydride Intermediates of Electrocatalytic Hydrogen Production

Abstract

We report the use of variable scan rate cyclic voltammetry to detect transient CoIIIH and CoIIH intermediates of electrocatalytic H2 production by CoII(dmgBF2)2(CH3CN)2 and [CoII(PtBu2NPh2)(CH3CN)3]2+. In both cases, reduction of the CoIIIH intermediate was observed to coincide with the CoII/I couple, and the resulting CoIIH intermediate is protonated by acid to afford H2. Our studies indicate that in electrocatalytic H2 production, protonation of CoIIH is rate-limiting for CoII(dmgBF2)2(CH3CN)2, and protonation of CoI is rate-limiting for [CoII(PtBu2NPh2)(CH3CN)3]2+. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

Authors:
;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1324910
Report Number(s):
PNNL-SA-105261
Journal ID: ISSN 0002-7863; KC0307010
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of the American Chemical Society; Journal Volume: 138; Journal Issue: 26
Country of Publication:
United States
Language:
English
Subject:
cobalt; electrocatalysis; hydrogen

Citation Formats

Wiedner, Eric S., and Bullock, R. Morris. Electrochemical Detection of Transient Cobalt Hydride Intermediates of Electrocatalytic Hydrogen Production. United States: N. p., 2016. Web. doi:10.1021/jacs.6b04779.
Wiedner, Eric S., & Bullock, R. Morris. Electrochemical Detection of Transient Cobalt Hydride Intermediates of Electrocatalytic Hydrogen Production. United States. doi:10.1021/jacs.6b04779.
Wiedner, Eric S., and Bullock, R. Morris. Wed . "Electrochemical Detection of Transient Cobalt Hydride Intermediates of Electrocatalytic Hydrogen Production". United States. doi:10.1021/jacs.6b04779.
@article{osti_1324910,
title = {Electrochemical Detection of Transient Cobalt Hydride Intermediates of Electrocatalytic Hydrogen Production},
author = {Wiedner, Eric S. and Bullock, R. Morris},
abstractNote = {We report the use of variable scan rate cyclic voltammetry to detect transient CoIIIH and CoIIH intermediates of electrocatalytic H2 production by CoII(dmgBF2)2(CH3CN)2 and [CoII(PtBu2NPh2)(CH3CN)3]2+. In both cases, reduction of the CoIIIH intermediate was observed to coincide with the CoII/I couple, and the resulting CoIIH intermediate is protonated by acid to afford H2. Our studies indicate that in electrocatalytic H2 production, protonation of CoIIH is rate-limiting for CoII(dmgBF2)2(CH3CN)2, and protonation of CoI is rate-limiting for [CoII(PtBu2NPh2)(CH3CN)3]2+. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.},
doi = {10.1021/jacs.6b04779},
journal = {Journal of the American Chemical Society},
number = 26,
volume = 138,
place = {United States},
year = {Wed Jul 06 00:00:00 EDT 2016},
month = {Wed Jul 06 00:00:00 EDT 2016}
}