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

Abstract

The metallic 1T-MoS₂ has attracted considerable attention as an effective catalyst for hydrogen evolution reactions (HERs). However, the fundamental mechanism about the catalytic activity of 1T-MoS₂ and the associated phase evolution remain elusive and controversial. Herein, we prepared the most stable 1T-MoS₂ by hydrothermal exfoliation of MoS₂ nanosheets vertically rooted into rigid one-dimensional TiO₂ nanofibers. The 1T-MoS₂ 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.

Keywords: ab initio calculations; molybdenum disulfide; monolayers; phase transitions; photocatalysis.