Circumventing CO2Reduction Scaling Relations Over the Heteronuclear Diatomic Catalytic Pair

In the electrochemical CO2reduction reaction (CO2RR), CO2activation is always the first step, followed by the subsequent hydrogenation. The catalytic performance of CO2RR is intrinsically restricted by the competition between molecular CO2activation and CO2reduction product release. Here, we design a heteronuclear Fe1-Mo1dual-metal catalytic pair on ordered porous carbon that features a high catalytic performance for driving electrochemical CO2reduction to CO. Combining real-time near-ambient pressure X-ray photoelectron spectroscopy, operando 57Fe Mössbauer spectroscopy, and in situattenuated total reflectance surface-enhanced infrared absorption spectroscopy measurements with density functional theory calculations, chemical adsorption of CO2is observed on the Fe1-Mo1catalytic pair through a bridge configuration, which prompts the bending of the CO2molecule for CO2activation and then facilitates the subsequent hydrogeneration reaction. More importantly, the dynamic adsorption configuration transition from the bridge configuration of CO2on Fe1-Mo1to the linear configuration of CO on the Fe1center results in breaking the scaling relationship in CO2RR, simultaneously promoting the CO2activation and the CO release.