Light‐Induced Electron Transfer in a NiFe Hydrogenase Opens a Photochemical Shortcut for Catalytic Dihydrogen Cleavage

NiFe hydrogenases catalyze the reversible cleavage of molecular hydrogen into protons and electrons. Here, we have studied the impact of temperature and illumination on an oxygen-tolerant and thermostable NiFe hydrogenase by IR and EPR spectroscopy. Equilibrium mixtures of two catalytic NiFe states, Ni