Augmenting the Performance of Hydrogenase for Aerobic Photocatalytic Hydrogen Evolution via Solvent Tuning

Abstract

AbstractThis work showcases the performance of [NiFeSe] hydrogenase from Desulfomicrobium baculatum for solar‐driven hydrogen generation in a variety of organic‐based deep eutectic solvents. Despite its well‐known sensitivity towards air and organic solvents, the hydrogenase shows remarkable performance under an aerobic atmosphere in these solvents when paired with a TiO2 photocatalyst. Tuning the water content further increases hydrogen evolution activity to a TOF of 60±3 s−1 and quantum yield to 2.3±0.4 % under aerobic conditions, compared to a TOF of 4 s−1 in a purely aqueous solvent. Contrary to common belief, this work therefore demonstrates that placing natural hydrogenases into non‐natural environments can enhance their intrinsic activity beyond their natural performance, paving the way for full water splitting using hydrogenases.