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Updated: Apr 7, 2026

Simple Methods for the Preparation of Non-noble Metal Bulk-electrodes for Electrocatalytic Applications
Published on: June 21, 2017
Proposed Ligand-Centered Electrocatalytic Hydrogen Evolution and Hydrogen Oxidation at a Noninnocent Mononuclear
Andrew Z Haddad1, Davinder Kumar1, Kagna Ouch Sampson1
1Department of Chemistry, University of Louisville, 2320 South Brook Street, Louisville, Kentucky 40292, United States.
Abstract:
The noninnocent coordinatively saturated mononuclear metal-thiolate complex ReL3 (L = diphenylphosphinobenzenethiolate) serves as an electrocatalyst for hydrogen evolution or hydrogen oxidation dependent on the presence of acid or base and the applied potential. ReL3 reduces acids to H2 in dichloromethane with an overpotential of 380 mV and a turnover frequency of 32 ± 3 s(-1). The rate law displays a second-order dependence on acid concentration and a first-order dependence on catalyst concentration with an overall third-order rate constant (k) of 184 ± 2 M(-2) s(-1). Reactions with deuterated acid display a kinetic isotope effect of 9 ± 1. In the presence of base, ReL3 oxidizes H2 with a turnover frequency of 4 ± 1 s(-1). The X-ray crystal structure of the monoprotonated species [Re(LH)L2](+), an intermediate in both catalytic H2 evolution and oxidation, has been determined. A ligand-centered mechanism, which does not require metal hydride intermediates, is suggested based on similarities to the redox-regulated, ligand-centered binding of ethylene to ReL3.
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