Exploring the photocatalytic properties and carrier dynamics of 2D Janus XMMX' (X = S, Se; M = Ga, In; and X' = Te) materials.

Recently, two-dimensional (2D) Janus structures have been extensively explored because of their robust electron mobility and unique photocatalytic properties. In spite of the increasing interest, the origin of high photocatalytic activities and the behaviors of photoinduced carriers in this kind of materials have not been well understood. Herein, we present a step-by-step protocol based on the first-principles calculations combined with the ab initio non-adiabatic molecular dynamics (NAMD) simulations to unveil the origin of high photocatalytic activity of highly stable typical 2D Janus XMMX' structures (X = S, Se; M = Ga, In; and X' = Te). Their band structures, optical properties, exciton binding energies, carrier effective masses, solar-to-hydrogen efficiency, hot carrier relaxation and recombination times, etc. have been calculated. We find that the difference between X and X' atoms on the two surfaces of the XMMX' monolayer not only builds an out-of-plane electric field, which significantly affects the charge distributions on the valence band maxima (VBM) and the conduction band minima (CBM) and subsequently decreases the exciton binding energy, but also transforms the indirect band structures of XM into the direct ones with well suitable energy gaps for visible-light absorption as well as endows the XMMX' structures with unequal electron and hole mobility, rapid hot carrier relaxation and slow electron-hole recombination processes on a timescale of tens of nanoseconds. The current work suggests that Janus XMMX' monolayers are good photocatalytic materials for overall water splitting and provides a guide to regulate the materials' properties for efficient energy harvesting and optoelectronic applications.