Hydrogen evolution based on the electrons/protons stored on amorphous TiO2

The hydrogen evolution reaction (HER) using recyclable mediator is being actively pursued as a route for solar energy conversion. Herein, we introduce a catalyst mediator (MoS2) that enables proton-coupled electron transfer (PCET) process on the recyclable TiO2 (H+–TiO2/e−) to a separate, catalytic hydrogen production step without requiring post-light energy input. This approach supplies a new insight to hydrogen evolution with the recyclable proton–electron pairs, stored at the semiconductor after the light irradiation. It was found that 80% of the electrons stored on TiO2 could be devoted to the reduction of H+ into H2 on MoS2 nanosheets in the dark. The electron transfer to MoS2 occurs at a rate of 455 μmol h−1 g−1 and 947 μmol h−1 g−1 in the dark and excited state, respectively.