Issue 7, 2011

A nickel–manganesecatalyst as a biomimic of the active site of NiFe hydrogenases: a combined electrocatalytical and DFT mechanistic study

Abstract

The dinuclear nickelmanganese complex [Ni(xbsms)Mn(CO)3(H2O)]+ (H2xbsms = 1,2-bis(4-mercapto-3,3-dimethyl-2-thiabutyl)benzene) is reported as a bio-inspired mimic of the active site of NiFe hydrogenases catalyzing hydrogen evolution from trifluoroacetic acid in DMF with an overpotential requirement of 860 mV. This is higher than that displayed by Ni–Ru systems [Canaguier et al., Chem.–Eur. J., 2009, 15, 9350–9364] but similar to that found for related noble metal free Ni–Fe mimics [Canaguier et al., Chem. Commun. 2010, 46, 5876–5878]. A combined electrochemical and theoretical (DFT) study suggests a heterolytic mechanism for hydrogen evolution from a hydride derivative. The structure of the active intermediate, with a bridging hydride ligand between Ni and Mn, resembles that of the Ni–C active state of NiFe hydrogenases.

Graphical abstract: A nickel–manganese catalyst as a biomimic of the active site of NiFe hydrogenases: a combined electrocatalytical and DFT mechanistic study

Supplementary files

Article information

Article type
Paper
Submitted
02 Dec 2010
Accepted
11 Jan 2011
First published
14 Feb 2011

Energy Environ. Sci., 2011,4, 2417-2427

A nickelmanganese catalyst as a biomimic of the active site of NiFe hydrogenases: a combined electrocatalytical and DFT mechanistic study

V. Fourmond, S. Canaguier, B. Golly, M. J. Field, M. Fontecave and V. Artero, Energy Environ. Sci., 2011, 4, 2417 DOI: 10.1039/C0EE00736F

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