Metalloid Coordination Reinforcing Electronic Synergy in Dual‐Atom Sites for Large‐Scale CO ₂ Electrolysis

Abstract

Abstract Reinforcing electronic synergy in dual‐atom catalysts (DACs) is critical yet challenging for boosting electrocatalytic CO 2 reduction (ECR) performances. Herein, we develop a versatile strategy introducing metalloid B to construct B,N co‐coordination dual sites featuring polarized (N–B) n bridges, enforcing electron delocalization between metal centers in DACs. Taking NiFe DACs as an example, the as‐obtained NiFe/BNC achieves 99% CO Faraday efficiency (FE CO ) and 55.7% full‐cell energy efficiency (200 mA cm −2 ) in a membrane electrode assembly (MEA) cell, markedly outperforming the common N‐coordinated counterpart (NiFe/NC) and representing state‐of‐the‐art performance. Moreover, upon scaling the cell area to 100 cm 2 , this catalyst maintains >95% FE CO during high‐current electrolysis at 1–6 A. Even at −53 °C, it sustains >98% FE CO across 50‐250 mA cm −2 , confirming the feasibility for in situ fuel production on Mars. Systematic investigations reveal B,N co‐coordination induces reversed electron transfer (Fe→Ni), distinct from weakly interacting NiFe/NC. This facilitates *COOH formation on electron‐enriched Ni sites and accelerated CO desorption from electron‐deficient Fe sites, synergistically enhancing ECR. Simultaneously, B sites promote water dissociation by adsorbing *OH intermediates, further boosting overall performance. Notably, this strategy shows broad versatility across Ni–Fe, Ni–Cu, Ni–Co, and Ni–Mn systems, opening new avenues for advanced DAC design.