Hybrid double-atom catalysts for the carbon monoxide reduction reaction: multiscale coupling of active site...

Hybrid double-atom catalysts (HDACs) provide a versatile platform to steer the carbon monoxide reduction reaction (CORR) toward C₂ products. However, the underlying principles connecting atomic-site electronics, electrolyte microenvironments and selectivity remain unclear. This work develops a mechanistic picture for carbon nitride (CN)-supported HDACs composed of 3d-metal and p-block-element dual centers by integrating density functional theory (DFT), ab initio molecular dynamics (AIMD), constant-potential simulations, and interpretable machine learning. Screening 36 HDACs identified stable dual centers with continuously tunable CO binding, which is governed by the d/p-band centers, metal-carbon bonding and adsorption-induced charge transfer. Mechanistic and constant-potential analyses reveal an intermediate dimer-strength regime and an operating window of around -0.4 V vs. RHE, where C-C coupling and proton-coupled electron transfer (PCET) kinetics are optimally aligned on NiB@CN. Explicit electrolyte modeling further shows that cation hydration, interfacial hydrogen-bond networks, and water orientation influence the balance between early *CO hydrogenation and *CO dimerization, with K⁺ giving the most favorable conditions among the modeled cations under the present computational conditions. Finally, an interpretable model built on ΔG _*CO, the metal-carbon bond length, and a quantitative charge-transfer metric captures the descriptor-activity trend within the present HDAC dataset and serves as a preliminary prescreening aid within this chemical space.