Circumventing CO<sub>2</sub> Reduction Scaling Relations Over the Heteronuclear Diatomic Catalytic Pair
Jie Ding, Fuhua Li, Jincheng Zhang, Qiao Zhang, Yuhang Liu, Weijue Wang, Wei Liu, Beibei Wang, Jun Cai, Xiaozhi Su, Hong Bin Yang, Xuan Yang, Yanqiang Huang, Yueming Zhai, Bin Liu
Abstract
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.