Synergistic Effect of Coordination Fields and Hydrosolvents on the Single-Atom Catalytic Property in H₂O₂ Synthesis: A Density Functional Theory Study

The design of high-performance single-atom catalysts (SACs) for two-electron oxygen reduction reaction (2e – ORR) is of great importance for the large-scale commercial application of H 2 O 2 electrosynthesis. Herein, utilizing the combination of density functional theory (DFT) calculation and ab initio molecular dynamic (AIMD) simulation, an effective computational framework was built to identify the critical role of coordination fields and hydrosolvents in the 2e – ORR catalytic properties of SAC-based two substrates [pristine γ-type graphyne (γ-GY) and B-doped γ-GY]. The screening calculations of 168 TM@(B-doped) γ-GY (TM = transition metal) revealed that both Co@B 1 -2-γ-GY and Pd@B 3 -2-γ-GY feature outstanding catalytic properties with low overpotentials (0.06, 0.02 V) and excellent stability. The electronic structure results uncovered that viewing from the coordination field, electron-deficient boron atoms can manipulate the electron back-donation effect ( d → π 2p * ) of the TM–O bond to mediate the H 2 O 2 property. Solvent effect calculations revealed that the hydrogen-bond (H-bond) framework plays an important role in the high selectivity of H 2 O 2 by facilitating the H transfer from water (>99.9 and 98.6% for Co@B 1 -2-γ-GY and Pd@B 3 -2-γ-GY), shedding light on the higher accuracy of an explicit solvent than that of an implicit one. This work will provide one way to better design high-selectivity SACs for H 2 O 2 synthesis effectively.