High-throughput DFT screening of transition metal-graphyne single-atom catalysts for oxygen reduction reaction

Transition metal (TM) clusters anchored on graphyne-supported transition metal carbides (TM-graphyne) exhibit rich design potential for catalytic applications owing to their highly exposed active sites, efficient atomic utilization, and the exceptional physicochemical properties of graphyne substrates. Despite these advantages, experimental validation remains limited for TM-graphyne catalysts, and critical knowledge gaps persist regarding optimal metal-support combinations for specific reactions. Here, we systematically investigate 30 TMgraphyne monolayers (TM = Cr-Zn, Mo-Ag) through integrated density functional theory (DFT) calculations and high-throughput screening, focusing on their oxygen reduction reaction (ORR) mechanisms. Our results reveal that catalytic activity is governed by the interaction strength between intermediates and TM centers, with d-band center modulation effectively mitigating strong intermediate adsorption. Among the candidates, Fe-graphyne and Mn-graphyne emerge as superior electrocatalysts, demonstrating remarkably low overpotentials (0.42 V and 0.59 V, respectively) while maintaining robust thermodynamic and electrochemical stability. This work establishes quantitative structure-activity relationships for TM-graphyne systems and provides a rational design framework for carbon-supported single-atom ORR catalysts, advancing fundamental understanding of graphynebased catalytic mechanisms.