Photo‐Enhanced Electronic Metal–Support Interaction Boosts Low‐Temperature Water–Gas Shift Reaction via Ni δ+ –O V –Ce 3+ Interfacial Redox Cycling

ABSTRACT Nickel (Ni) is an attractive non‐noble‐metal catalyst for the water‐gas shift reaction (WGSR), yet strong CO adsorption and competing methanation severely limit its activity and selectivity. Herein, we develop a series of NiCe layered double hydroxide‐derived catalysts (NCO‐ T ) through reduction‐induced Ni exsolution. The optimized NCO‐450 catalyst achieves 92.53% CO conversion and an H 2 production rate of 103.24 µmol·g cat −1 ·s −1 at ambient pressure and a catalyst temperature of 83°C. In situ spectroscopic analyses and theoretical calculations reveal that isolated interfacial oxygen vacancies (O V s) stabilize the active Ni δ+ ─O V ─Ce 3+ motif responsible for the superior WGSR performance. Photoexcitation‐induced directional interfacial charge transfer from Ni to CeO 2‐ x enhances the electronic metal–support interaction and continuously regenerates this active interfacial state, thereby moderating CO adsorption, promoting H 2 O activation, and suppressing competing methanation. This work offers a rational design strategy for developing low‐cost transition‐metal catalysts with superior low‐temperature activity and high selectivity.