Circumventing CO₂ Reduction Scaling Relations Over the Heteronuclear Diatomic Catalytic Pair

Inthe electrochemical CO2 reduction reaction(CO2RR), CO2 activation is always the firststep, followedby the subsequent hydrogenation. The catalytic performance of CO2RR is intrinsically restricted by the competition betweenmolecular CO2 activation and CO2 reduction productrelease. Here, we design a heteronuclear Fe-1-Mo-1 dual-metal catalytic pair on ordered porous carbon that featuresa high catalytic performance for driving electrochemical CO2 reduction to CO. Combining real-time near-ambient pressure X-rayphotoelectron spectroscopy, operando Fe-57 Mo''ssbauerspectroscopy, and in situ attenuated total reflectancesurface-enhanced infrared absorption spectroscopy measurements withdensity functional theory calculations, chemical adsorption of CO2 is observed on the Fe-1-Mo-1 catalyticpair through a bridge configuration, which prompts the bending ofthe CO2 molecule for CO2 activation and thenfacilitates the subsequent hydrogeneration reaction. More importantly,the dynamic adsorption configuration transition from the bridge configurationof CO2 on Fe-1-Mo-1 to the linear configurationof CO on the Fe-1 center results in breaking the scalingrelationship in CO2RR, simultaneously promoting the CO2 activation and the CO release.