Coordination-controlled OH adsorption in main-group homonuclear dual-atom catalysts for H2O2 electrosynthesis: a DFT
Zelong Xu1, Zhe Liu2, Cong Wei2
1School of Materials Science and Engineering, Jiangsu University, Zhenjiang, China, 212013.
None:
Electrochemical synthesis of H2O2via the two-electron water oxidation reaction (2e- WOR) is a promising strategy for decentralized production. However, precise control over OH* adsorption remains elusive. Coordination engineering, by tuning the metal center nitrogen coordination numbers, enables precise regulation of OH* adsorption toward the thermodynamic optimum. Herein, first-principles calculations reveal that the activity of homonuclear main-group dual-atom catalysts can be effectively optimized through coordination engineering. Reducing N-coordination numbers modulates the p-p orbital hybridization strength between the metal centers and the adsorbed OH*, steering OH* adsorption toward the volcano optimum. For systems with initially overly strong OH* adsorption (e.g., Bi, Ga, and Ge), this reduction decreases the p-p overlap area, weakening the hybridization, thereby weakening binding, whereas for weakly adsorbing systems (Tl), it enhances the p-p overlap area, strengthening the hybridization, thereby strengthening adsorption. The tuning strategy is theoretically predicted using a Tl-based catalyst with a near-ideal overpotential of 0.01 V. These findings establish coordination engineering as a universal approach for the rational design of high-performance H2O2 catalysts.
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