How can the Dual‐atom Catalyst FeCo–NC Surpass Single‐atom Catalysts Fe–NC/Co–NC in CO2RR? – CO Intermediate Assisted Promotion via a Synergistic Effect

Atomically dispersed catalysts are widely adopted in CO 2 reduction reaction (CO 2 RR) due to maximal atomic utilization and high catalytic activity. Dual‐atom catalysts (DACs), with more dispersed active sites and distinct electronic structures compared with single‐atom catalysts (SACs), may exhibit diverse catalytic performance. Herein, the DAC FeCo–NC and SAC Fe–NC/Co–NC are employed as probes to explore DACs advantage in CO 2 RR. Results show that the moderate interaction between the dual‐atom center and N coordination balances structural stability and catalytic activity. CO is the only product on Fe–NC/Co–NC, and the high limiting potentials from −1.22 to −1.67 V inhibit further reduction. FeCo–NC assisted with CO intermediate exhibits low limiting potentials of −0.64 V for both CH 3 OH and CH 4 , comparable to those on Cu‐based catalysts. Under circumstance of applied potentials, CO 2 RR on FeCo–NC has greater advantages in yielding CH 3 OH and CH 4 than that on Fe–NC/Co–NC, and hydrogen evolution reaction is severely inhibited. The intrinsic essence is that dual‐atom center can provide large spin‐polarization and multi‐electron transfer capability, rendering CO intermediates as effective electronic and geometric modifiers in CO 2 RR. This work highlights FeCo–NC as a high‐performance CO 2 RR catalyst toward deep‐reduction C1 products and elucidates CO intermediate assisted promotion mechanism via a dual‐atom synergistic effect.