How Light-Harvesting Semiconductors Can Alter the Bias of Reversible Electrocatalysts in Favor of H 2 Production and CO 2 Reduction

The most efficient catalysts for solar fuel production should operate close to reversible potentials, yet possess a bias for the fuel-forming direction. Protein film electrochemical studies of Ni-containing carbon monoxide dehydrogenase and [NiFeSe]-hydrogenase, each a reversible electrocatalyst, sh...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2013-10, Vol.135 (40), p.15026-15032
Main Authors: Bachmeier, Andreas, Wang, Vincent C. C., Woolerton, Thomas W., Bell, Sophie, Fontecilla-Camps, Juan C., Can, Mehmet, Ragsdale, Stephen W., Chaudhary, Yatendra S., Armstrong, Fraser A.
Format: Article
Language:English
Subjects:
Aldehyde Oxidoreductases
Biochemistry, Molecular Biology
Biomimetics
Carbon Dioxide
Catalysis
Electrochemistry
Hydrogen
Hydrogenase
Life Sciences
Light
Models, Molecular
Multienzyme Complexes
Oxidation-Reduction
Photosynthesis
Protein Conformation
Semiconductors
Structural Biology
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Summary:The most efficient catalysts for solar fuel production should operate close to reversible potentials, yet possess a bias for the fuel-forming direction. Protein film electrochemical studies of Ni-containing carbon monoxide dehydrogenase and [NiFeSe]-hydrogenase, each a reversible electrocatalyst, show that the electronic state of the electrode strongly biases the direction of electrocatalysis of CO2/CO and H(+)/H2 interconversions. Attached to graphite electrodes, these enzymes show high activities for both oxidation and reduction, but there is a marked shift in bias, in favor of CO2 or H(+) reduction, when the respective enzymes are attached instead to n-type semiconductor electrodes constructed from CdS and TiO2 nanoparticles. This catalytic rectification effect can arise for a reversible electrocatalyst attached to a semiconductor electrode if the electrode transforms between semiconductor- and metallic-like behavior across the same narrow potential range (
ISSN:0002-7863
1520-5126
DOI:10.1021/ja4042675