Light-Driven Hydrogen Evolution by Nickel-Substituted Rubredoxin - PubMed (original) (raw)

. 2017 Nov 23;10(22):4424-4429.

doi: 10.1002/cssc.201701627. Epub 2017 Oct 25.

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Light-Driven Hydrogen Evolution by Nickel-Substituted Rubredoxin

Michael J Stevenson et al. ChemSusChem. 2017.

Abstract

An enzymatic system for light-driven hydrogen generation has been developed through covalent attachment of a ruthenium chromophore to nickel-substituted rubredoxin (NiRd). The photoinduced activity of the hybrid enzyme is significantly greater than that of a two-component system and is strongly dependent on the position of the ruthenium phototrigger relative to the active site, indicating a role for intramolecular electron transfer in catalysis. Steady-state and time-resolved emission spectra reveal a pathway for rapid, direct quenching of the ruthenium excited state by nickel, but low overall turnover numbers suggest initial electron transfer is not the rate-limiting step. This approach is ideally suited for detailed mechanistic investigations of catalysis by NiRd and other molecular systems, with implications for generation of solar fuels.

Keywords: electron transfer; emission spectroscopy; photocatalysis; ruthenium; solar fuels.

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