Light-Driven Hydrogen Evolution Reaction Catalyzed by a Molybdenum-Copper Artificial Hydrogenase - Archive ouverte HAL Access content directly
Journal Articles Journal of the American Chemical Society Year : 2023

Light-Driven Hydrogen Evolution Reaction Catalyzed by a Molybdenum-Copper Artificial Hydrogenase

Abstract

Orange Protein (Orp) is a small bacterial metalloprotein of unknown function that harbors a unique molybdenum/copper (Mo/Cu) heterometallic cluster, [S2MoS2CuS2MoS2]3−. In this paper, the performance of Orp as a catalyst for the photocatalytic reduction of protons into H2 has been investigated under visible light irradiation. We report the complete biochemical and spectroscopic characterization of holo-Orp containing the [S2MoS2CuS2MoS2]3− cluster, with docking and molecular dynamics simulations suggesting a positively charged Arg, Lys-containing pocket as the binding site. Holo-Orp exhibits an excellent photocatalytic activity, in the presence of ascorbate as the sacrificial electron donor and [Ru(bpy)3]Cl2 as the photosensitizer, for hydrogen evolution with a maximum turnover number of 890 after 4 hours irradiation. DFT calculations were used to propose a consistent reaction mechanism in which the terminal sulfur atoms are playing a key role in promoting H2 formation. A series of dinuclear [S2MS2M’S2MS2](4n)− clusters, with M = MoVI, WVI and M’(n+) = CuI, FeI, NiI, CoI , ZnII, CdII were assembled in Orp, leading to different M/M’-Orp versions which are shown to display catalytic activity, with the Mo/Fe-Orp catalyst giving a remarkable TON of 1150 after 2.5 hours reaction and an initial turnover frequency (TOF°) of 800 h-1 establishing a record among previously reported artificial hydrogenases.
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Dates and versions

hal-04128647 , version 1 (14-06-2023)

Identifiers

Cite

Raphaël J Labidi, Bruno Faivre, Philippe Carpentier, Giulia Veronesi, Albert Solé- Daura, et al.. Light-Driven Hydrogen Evolution Reaction Catalyzed by a Molybdenum-Copper Artificial Hydrogenase. Journal of the American Chemical Society, 2023, 145 (25), pp.13640-13649. ⟨10.1021/jacs.3c01350⟩. ⟨hal-04128647⟩
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