Metalloid Coordination Reinforcing Electronic Synergy in Dual‐Atom Sites for Large‐Scale CO <sub>2</sub> Electrolysis
Tingting Cui, Yuchao Wang, Rufan Xu, Mengyang Duan, Yanming Yu, Longqian Wang, Guanjie Li, Haiming Han, Haozhi Wang, Yunchuan Tu, Yongpeng Lei, Ming Xu, Dingsheng Wang
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.