A Systematic Theoretical Study on Electronic Interaction in Cu-based Single-Atom Alloys

[Image: see text] A meticulous understanding of the electronic structure of catalysts may provide new insight into catalytic performances. Here, we present a d–d interaction model to systematically study the electronic interaction in Cu-based single-atom alloys. We refine three types of electronic interactions according to the position of the antibonding state relative to the Fermi level. Moreover, we also find a special phenomenon in Mn-doped single-atom alloys in which no obvious electronic interaction is found, and the doped Mn metal seems to be a free atom. Then, taking Hf/Mn-doped single-atom alloys as an example, we discuss the electronic structure based on the density of states, charge transfer, crystal orbital Hamilton population, and wavefunctions. To support the proposed model and help analyze the data, we perform an energetic analysis of water dissociation in the water-gas shift reaction. The calculation results well confirm the d–d interaction model, where alloys with the position of the antibonding state close to the Fermi level exhibit excellent water dissociation ability in the water-gas shift reaction. However, the catalytic performance of the Mn-doped alloy is unsatisfactory, which is caused by its own special phenomenon.