Efficient and Robust Heterostructure CeZrOx/NiO‐Ni Inverse Catalyst for Sustainable Photothermal CO2 Methanation

ABSTRACT Photothermal CO2 methanation offers a route to store renewable energy as synthetic methane, yet conventional Ni catalysts typically require intense light or auxiliary heating and show poor tolerance to intermittency. Here, we report a CeZrOx/NiO‐Ni inverse catalyst via a heterostructure engineering strategy, featuring a protective NiO interlayer. This tailored architecture achieves 83% single‐pass CO2 conversion with >99% CH4 selectivity under 0.71 W cm−2 irradiation in a continuous‐flow system, without external heating. Notably, it delivers a CH4 space‐time yield of 464 mmol·gcat−1·h−1 under natural concentrated sunlight and maintains robust performance over repeated light‐dark cycles, extended air storage, and 100‐g scaled synthesis, demonstrating its potential compatibility with intermittent renewable energy. Mechanistic studies reveal that the sub‐nanometer NiO layer on Ni domains enhances LSPR‐induced heating and hot‐carrier injection while establishing a favorable CeZrOx/NiO‐Ni band alignment for charge separation. This heterointerface further promotes CO2 activation via *COOH intermediates and electron‐mediated pathways, thereby amplifying photothermal synergy under low‐intensity illumination. This work highlights the critical role of interfacial engineering in advancing solar‐driven energy conversion and provides a catalyst‐level design strategy that could help bridge lab‐scale innovation and future practical applications.