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.

Automated summary

In this study, a Fe-1-Mo-1 heteronuclear dual-metal catalyst on ordered porous carbon was designed for driving electrochemical CO2 reduction to CO with high catalytic performance. The chemical adsorption of CO2 on the Fe-1-Mo-1 catalytic pair promotes CO2 activation and subsequent hydrogeneration reaction through a bridge configuration. The transition of adsorption configuration from bridge to linear configuration breaks the scaling relationship in CO2RR, leading to enhanced CO2 activation and CO release.