Boosting C=O Bond Scissoring Over a Pyridinic Nitrogen‐Modified Cu–MoC Interface for High‐Efficiency CO ₂ Hydrogenation to CO

ABSTRACT Reverse water‐gas shift (RWGS) reaction‐aided sustainable CO 2 conversion has emerged as one promising and effective approach for simultaneously mitigating climate change and solidifying energy security. Molybdenum carbide‐based catalysts demonstrate excellent selectivity for sustainably transforming CO 2 into CO product, but harsh carburization syntheses and insufficient catalytic activity and stability significantly hinder their related commercial applications. Herein, a facile “inside‐out” synthesis strategy was proposed to fabricate dispersed Cu clusters on sub‐2 nm α‐MoC nanoislands confined in pyridinic nitrogen‐doped carbon (Cu‐MoC/NC). This catalyst achieves the highest CO 2 conversion rate of 2583.4 mmol CO2 g cat −1 h −1 compared to those of all reported Mo‐based catalysts, and maintains excellent catalytic stability for 500 h under a low H 2 partial pressure. Combined with X‐ray absorption spectroscopy (XAS) and density functional theory (DFT) calculations, the electronegativity of pyridinic nitrogen intensifies the electron deficiency of α‐MoC and strengthens the chemisorption of Cu clusters on α‐MoC nanoislands surface, facilitating the electronic interaction and stability of Cu–MoC interface. This pyridinic nitrogen‐modified Cu–MoC interface promotes the CO 2 bridged adsorption at the interface and thus boosts C=O bond scissoring, inducing the transition of rate‐limiting step and energy barrier reduction of the key intermediates. This interfacial engineering provides a sustainable and efficient strategy for improving both catalytic activity and stability of RWGS reaction to transform CO 2 into value‐added fuels and chemicals.