Atomic Insights for Optimum and Excess Doping in Photocatalysis: A Case Study of Few‐Layer Cu‐ZnIn2S4

Abstract Herein, an example of Cu‐doped few‐layer ZnIn 2 S 4 nanosheets is used to reveal the origin of optimum and excess doping for photocatalysts at atomic level. Results show that the metal‐S 4 coordination maintains well with 0.5 wt% Cu substituted Zn atoms in the lattice. The introduced Cu atoms bring electronic acceptor states close to the valence band (VB) maximum and thus ensures higher charge density and efficient carrier transport, resulting in an optimum hydrogen evolution rate of 26.2 mmol h −1 g −1 and an apparent quantum efficiency of 4.76% at 420 nm. However, a distorted atomic structure and largely upshift of VB maximum with Cu‐S 3.6 coordination are found with excess doping concentration (3.6 wt%). These bring the heavy charge recombination and consequentially dramatic reduced activity. This work provides a new insight into elemental doping study and takes an important step toward the development of ultrathin 2D photocatalysts.