Impact of surface patterning on the reactivity of Cu2O (100) under working conditions: Ab initio analysis of CO2 adsorption and activation

This research intensively explored the impact of surface patterning on Cu 2 O (100) reactivity under real conditions. Modeling studies were conducted on CO 2 adsorption and dissociation post-patterning treatments. Ab initio molecular dynamics (AIMD) simulations verified the stability of three increasingly deep, plausible groove structures. From the perspective of electronic structure, the shift of the d‐band center towards the Fermi level indicated that the groove configurations were beneficial to the adsorption of gas molecules, which was also verified by the adsorption energy calculation results. By analyzing the Partial Density of States (PDOS) and Bader charge, it was revealed that charge transfer occurred between CO 2 and the groove surfaces, and CO 2 was activated by the strong interaction with the patterned surface. The dissociation energy barrier calculated by CI-NEB method suggested that the dissociation ability of CO 2 was inversely proportional to its adsorption capacity. Subsequently, by calculating the reaction rate constant and analyzing the competitive relationship between the Hydrogen Evolution Reaction (HER) and dissociation reactions, it was comprehensively determined that the G3 patterned configuration was more conducive to the occurrence of CO 2 dissociation reactions. Our calculations clarified the differences in CO 2 adsorption and dissociation among various configurations and demonstrated the crucial role played by unsaturated three-coordinated oxygen atoms in the process of CO 2 adsorption and dissociation, which was contrary to the traditional view that the exposure of oxygen atoms was unfavorable for adsorption. This research is closely related to the current development and design of efficient catalysts for the capture and recovery of gaseous pollutants. • The strategic patterning regulates the electronic structural features of the Cu 2 O (100) surface. • The exposure of tri-coordinate oxygen atoms under working conditions facilitates the activation and dissociation of CO 2 . • Tailoring the type of surface exposure can effectively modulate the catalytic performance.