Issue 10, 2015

Application of the energetic span model to the electrochemical catalysis of proton reduction by a diiron azadithiolate complex

Abstract

Computational methods, such as DFT calculations, have emerged as a powerful tool to study the homogeneous catalysis of electrochemical reactions involved in renewable fuel production. Here, we report an adaptation of the energetic span model to obtain, from DFT calculations, key metrics of the catalysis of electrochemical H2 production by the diiron azadithiolate complex [Fe2(μ-SCH2NHCH2S)(CO)6] (1). The main advantage of our approach is that both thermodynamic and kinetic effects on the turnover frequency (TOF) can be computed in a simple way. By taking into account the influence of the electrode potential on TOF determining intermediates (TDI) and TOF determining transition states (TDTS), we calculated a TOF vs. overpotential relationship that shows three different kinetic regimes. This finding is consistent with the catalytic mechanism derived from the analysis of voltammetric responses of 1 in the presence of tosic acid.

Graphical abstract: Application of the energetic span model to the electrochemical catalysis of proton reduction by a diiron azadithiolate complex

Supplementary files

Article information

Article type
Paper
Submitted
27 Mar 2015
Accepted
07 Aug 2015
First published
11 Aug 2015

New J. Chem., 2015,39, 8073-8079

Author version available

Application of the energetic span model to the electrochemical catalysis of proton reduction by a diiron azadithiolate complex

M. Bourrez and F. Gloaguen, New J. Chem., 2015, 39, 8073 DOI: 10.1039/C5NJ00770D

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