Self‐Optimization of the Active Site of Molybdenum Disulfide by an Irreversible Phase Transition during Photocatalytic Hydrogen Evolution

Abstract The metallic 1T‐MoS 2 has attracted considerable attention as an effective catalyst for hydrogen evolution reactions (HERs). However, the fundamental mechanism about the catalytic activity of 1T‐MoS 2 and the associated phase evolution remain elusive and controversial. Herein, we prepared the most stable 1T‐MoS 2 by hydrothermal exfoliation of MoS 2 nanosheets vertically rooted into rigid one‐dimensional TiO 2 nanofibers. The 1T‐MoS 2 can keep highly stable over one year, presenting an ideal model system for investigating the HER catalytic activities as a function of the phase evolution. Both experimental studies and theoretical calculations suggest that 1T phase can be irreversibly transformed into a more active 1T′ phase as true active sites in photocatalytic HERs, resulting in a “catalytic site self‐optimization”. Hydrogen atom adsorption is the major driving force for this phase transition.