@article{Pastor:2017:10.1038/ncomms14280,
author = {Pastor, E and Le, Formal F and Mayer, MT and Tilley, SD and Gratzel, M and Francas, Forcada L and Mesa, CA and Durrant, JR},
doi = {10.1038/ncomms14280},
journal = {Nature Communications},
title = {Spectroelectrochemical analysis of the mechanism of (photo)electrochemical hydrogen evolution at a catalytic interface},
url = {http://dx.doi.org/10.1038/ncomms14280},
volume = {8},
year = {2017}
}

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TY  - JOUR
AB  - 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 thehomolytic reductive elimination of hydrogen.
AU  - Pastor,E
AU  - Le,Formal F
AU  - Mayer,MT
AU  - Tilley,SD
AU  - Gratzel,M
AU  - Francas,Forcada L
AU  - Mesa,CA
AU  - Durrant,JR
DO  - 10.1038/ncomms14280
PY  - 2017///
SN  - 2041-1723
TI  - Spectroelectrochemical analysis of the mechanism of (photo)electrochemical hydrogen evolution at a catalytic interface
T2  - Nature Communications
UR  - http://dx.doi.org/10.1038/ncomms14280
UR  - http://hdl.handle.net/10044/1/42723
VL  - 8
ER  - 

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