Interfacial Electron Potential Well Facilitates the Design of Cobalt Phosphide Heterojunctions for Hydrogen Evolution

Abstract The interfacial electron modulation of electrocatalysts is an effective way to realize efficient hydrogen production, which is of great importance for future renewable energy systems. However, systematic theory‐guided design of catalysts in heterojunction coupling is lacking. In this work, a multi‐level theoretical calculation is performed to screen optimal candidates to form a heterojunction with CoP (101) surface for electrocatalytic hydrogen production. To overcome the weak adsorption of H + on CoP (101), rational design of electrons potential well at the heterojunction interface can effectively enhance the hydrogen adsorption. All p‐type cobalt‐based phosphides are considered potential candidates at the beginning. After screening for conductivity, stability, interface matching screening, and Δ G H* evaluation, the CoP/Co 2 P‐H system is identified to be able to display optimal hydrogen production performance. To verify the theoretical design, CoP, CoP/Co 2 P‐H, and CoP/Co 2 P‐O are synthesized and the electrochemical analysis is carried out. The hydrogen evolution reaction (HER) performance is consistent with the prediction. This work utilizes the electron potential well effect and multi‐level screening calculations to design highly efficient heterojunction catalysts, which can provide useful theoretical guidance for the rational design of heterojunction‐type catalysts.