Spectroelectrochemical Analysis of the Mechanism of (photo)electrochemical Hydrogen Evolution at a Catalytic Interface

Overview

Journal Nat Commun

Specialty Biology

Date 2017 Feb 25

PMID 28233785

Citations 18

Authors

Ernest Pastor

Florian Le Formal

Matthew T Mayer

S David Tilley

Laia Francas

Camilo A Mesa

Michael Gratzel

James R Durrant

Affiliations

Soon will be listed here.

Abstract

Multi-electron heterogeneous catalysis is a pivotal element in the (photo)electrochemical generation of solar fuels. However, mechanistic studies of these systems are difficult to elucidate by means of electrochemical methods alone. Here we report a spectroelectrochemical analysis of hydrogen evolution on ruthenium oxide employed as an electrocatalyst and as part of a cuprous oxide-based photocathode. We use optical absorbance spectroscopy to quantify the densities of reduced ruthenium oxide species, and correlate these with current densities resulting from proton reduction. This enables us to compare directly the catalytic function of dark and light electrodes. We find that hydrogen evolution is second order in the density of active, doubly reduced species independent of whether these are generated by applied potential or light irradiation. Our observation of a second order rate law allows us to distinguish between the most common reaction paths and propose a mechanism involving the homolytic reductive elimination of hydrogen.

Citing Articles

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