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Spectroelectrochemical analysis of the mechanism of (photo)electrochemical hydrogen evolution at a catalytic interface

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Title: Spectroelectrochemical analysis of the mechanism of (photo)electrochemical hydrogen evolution at a catalytic interface
Authors: Pastor, E
Le Formal, F
Mayer, MT
Tilley, SD
Gratzel, M
Francas Forcada, L
Mesa, CA
Durrant, JR
Item Type: Journal Article
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 pectroelectrochemical 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 directly compare 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.
Issue Date: 24-Feb-2017
Date of Acceptance: 9-Nov-2016
URI: http://hdl.handle.net/10044/1/42723
DOI: https://dx.doi.org/10.1038/ncomms14280
ISSN: 2041-1723
Publisher: Nature Publishing Group
Journal / Book Title: Nature Communications
Volume: 8
Copyright Statement: © The Author(s) 2017. This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/
Sponsor/Funder: Commission of the European Communities
Funder's Grant Number: 291482
Keywords: Science & Technology
Multidisciplinary Sciences
Science & Technology - Other Topics
TRANSFER RATE CONSTANTS
FREE-ENERGY DEPENDENCE
ELECTRON-TRANSFER
ABSORPTION-SPECTROSCOPY
MOLECULAR CATALYSTS
OXIDE ELECTRODES
CHARGE-TRANSFER
H-2 PRODUCTION
ELECTROCATALYSIS
RUO2
MD Multidisciplinary
Publication Status: Published
Article Number: 14280
Appears in Collections:Chemistry
Faculty of Natural Sciences



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