Selecting dual atomic clusters supported on two-dimensional biphenylene with significantly optimized capability to reduce carbon monoxide

Abstract

Compared to single-atom and high-selectivity catalysts, dual atomic clusters can facilitate multi-step catalysis, which is beneficial for the CO reduction reaction (CORR). Recently, a novel porous biphenylene (BPN) monolayer with excellent stability and superior electronic transport properties was experimentally synthesized, offering promising conductivity for efficient CORR. Through density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations, in this study, we comprehensively investigated the structure–activity relationships of 28 dual-atom catalysts (DACs) composed of 3d, 4d, and 5d transition metal (TM) dimers anchored on BPN (TM₂@BPN). Among the 28 TM₂@BPN candidates, four DACs were identified based on a five-step screening strategy to surpass the activity benchmarks for metals and achieve efficient CORR. Specifically, Fe₂@BPN and Ir₂@BPN can produce methane (CH₄) with a limiting potential of 0.62 V and 0.53 V, respectively, while Ni₂@BPN and Cu₂@BPN can produce ethanol (CH₃CH₂OH) and ethylene (CH₂CH₂) with a limiting potential of 0.59 V and 0.46 V and kinetic barriers of 0.60 eV and 0.04 eV, respectively. This work not only offers a viable strategy for rationally designing CORR catalysts but also paves the way for the rapid screening of efficient DACs for CORR and other electrochemical reactions.