How light-harvesting semiconductors can alter the bias of reversible electrocatalysts in favor of H2 production and CO2 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, 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 (<0.25 V) that the electrocatalytic current switches between oxidation and reduction.
Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford , South Parks Road, Oxford OX1 3QR, Oxfordshire, United Kingdom.
Andreas
A
Bachmeier
Vincent C C
VC
Wang
Thomas W
TW
Woolerton
Sophie
S
Bell
Juan C
JC
Fontecilla-Camps
Mehmet
M
Can
Stephen W
SW
Ragsdale
Yatendra S
YS
Chaudhary
Fraser A
FA
Armstrong
D000445:Aldehyde Oxidoreductases / Q000737:chemistry / Q000378:metabolism; D032701:Biomimetics / Q000295:instrumentation / Q000379:methods*; D002245:Carbon Dioxide / Q000737:chemistry*; D002384:Catalysis; D004563:Electrochemistry; D006859:Hydrogen / Q000737:chemistry*; D006864:Hydrogenase / Q000737:chemistry / Q000378:metabolism; D008027:Light; D008958:Models, Molecular; D009097:Multienzyme Complexes / Q000737:chemistry / Q000378:metabolism; D010084:Oxidation-Reduction; D010788:Photosynthesis; D011487:Protein Conformation; D012666:Semiconductors
D009097:Multienzyme Complexes; D002245:Carbon Dioxide; D006859:Hydrogen; C058560:nickel-iron-selenium hydrogenase; D006864:Hydrogenase; D000445:Aldehyde Oxidoreductases; C019823:carbon monoxide dehydrogenase