Circumventing CO 2 Reduction Scaling Relations Over the Heteronuclear Diatomic Catalytic Pair.

In the electrochemical CO 2 reduction reaction (CO 2 RR), CO 2 activation is always the first step, followed by the subsequent hydrogenation. The catalytic performance of CO 2 RR is intrinsically restricted by the competition between molecular CO 2 activation and CO 2 reduction product release. Here, we design a heteronuclear Fe 1 -Mo 1 dual-metal catalytic pair on ordered porous carbon that features a high catalytic performance for driving electrochemical CO 2 reduction to CO. Combining real-time near-ambient pressure X-ray photoelectron spectroscopy, operando 57 Fe Mössbauer spectroscopy, and in situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy measurements with density functional theory calculations, chemical adsorption of CO 2 is observed on the Fe 1 -Mo 1 catalytic pair through a bridge configuration, which prompts the bending of the CO 2 molecule for CO 2 activation and then facilitates the subsequent hydrogeneration reaction. More importantly, the dynamic adsorption configuration transition from the bridge configuration of CO 2 on Fe 1 -Mo 1 to the linear configuration of CO on the Fe 1 center results in breaking the scaling relationship in CO 2 RR, simultaneously promoting the CO 2 activation and the CO release.