A matrix of heterobimetallic complexes for interrogation of hydrogen evolution reaction electrocatalysts.

ABSTRACT: Experimental and computational studies address key questions in a structure-function analysis of bioinspired electrocatalysts for the HER. Combinations of NiN2S2 or [(NO)Fe]N2S2 as donors to (η5-C5H5)Fe(CO)+ or [Fe(NO)2]+/0 generate a series of four bimetallics, gradually "softened" by increasing nitrosylation, from 0 to 3, by the non-innocent NO ligands. The nitrosylated NiFe complexes are isolated and structurally characterized in two redox levels, demonstrating required features of electrocatalysis. Computational modeling of experimental structures and likely transient intermediates that connect the electrochemical events find roles for electron delocalization by NO, as well as Fe-S bond dissociation that produce a terminal thiolate as pendant base well positioned to facilitate proton u

SUBMITTER: Ghosh P 

PROVIDER: S-EPMC5858031 | biostudies-literature | 2017 Dec

REPOSITORIES: biostudies-literature