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Wiring of Photosystem II to Hydrogenase for Photoelectrochemical Water Splitting.

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Mersch, Dirk 
Lee, Chong-Yong 
Zhang, Jenny Zhenqi 
Brinkert, Katharina 
Fontecilla-Camps, Juan C 


In natural photosynthesis, light is used for the production of chemical energy carriers to fuel biological activity. The re-engineering of natural photosynthetic pathways can provide inspiration for sustainable fuel production and insights for understanding the process itself. Here, we employ a semiartificial approach to study photobiological water splitting via a pathway unavailable to nature: the direct coupling of the water oxidation enzyme, photosystem II, to the H2 evolving enzyme, hydrogenase. Essential to this approach is the integration of the isolated enzymes into the artificial circuit of a photoelectrochemical cell. We therefore developed a tailor-made hierarchically structured indium-tin oxide electrode that gives rise to the excellent integration of both photosystem II and hydrogenase for performing the anodic and cathodic half-reactions, respectively. When connected together with the aid of an applied bias, the semiartificial cell demonstrated quantitative electron flow from photosystem II to the hydrogenase with the production of H2 and O2 being in the expected two-to-one ratio and a light-to-hydrogen conversion efficiency of 5.4% under low-intensity red-light irradiation. We thereby demonstrate efficient light-driven water splitting using a pathway inaccessible to biology and report on a widely applicable in vitro platform for the controlled coupling of enzymatic redox processes to meaningfully study photocatalytic reactions.



Catalysis, Chromatography, Gas, Electrochemistry, Electrodes, Electrons, Hydrogen, Hydrogenase, Light, Oxidation-Reduction, Oxygen, Photochemistry, Photosynthesis, Photosystem II Protein Complex, Proteobacteria, Solar Energy, Synechococcus, Thermodynamics, Tin Compounds, Water

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J Am Chem Soc

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American Chemical Society (ACS)
Biotechnology and Biological Sciences Research Council (BB/K010220/1)
Engineering and Physical Sciences Research Council (EP/H00338X/2)
Engineering and Physical Sciences Research Council (EP/G037221/1)
This work was supported by the U.K. Engineering and Physical Sciences Research Council (EP/H00338X/2 to E.R. and EP/G037221/1, nanoDTC, to D.M.), the UK Biology and Biotechnological Sciences Research Council (BB/K002627/1 to A.W.R. and BB/K010220/1 to E.R.), a Marie Curie Intra-European Fellowship (PIEF-GA-2013-625034 to C.Y.L), a Marie Curie International Incoming Fellowship (PIIF-GA-2012-328085 RPSII to J.J.Z) and the CEA and the CNRS (to J.C.F.C.). A.W.R. holds a Wolfson Merit Award from the Royal Society.