Light‐Driven Reverse Water Gas Shift Reaction with 1000‐H Stability on High‐Entropy Alloy Catalysts

Abstract Highly stable and active catalysts are of significant importance and a longstanding challenge for a number of industrial chemical transformations. Here, motivated by the principle of the high entropy‐stabilized structure, high‐entropy alloy‐loaded porous TiO ₂ as an efficient and sintering‐resistant catalyst for the light‐driven reverse water gas‒shift reaction without external heating is synthesized. The optimized CoNiCuPdRu/TiO ₂ catalyst exhibits a long‐term stability of 1000 h (1.23 mol g _metal ⁻¹ h ⁻¹ CO production rate, >99% high selectivity). In situ characterizations confirm that the slow diffusion effect of high‐entropy alloys endows the catalyst with excellent structural stability. The CO adsorption measurements and theoretical calculations consolidate that the hydrogen surface coverage weakens CO adsorption on the catalyst surface. Two major problems of catalyst deactivation − sintering and poisoning, are handled in one case, which synergistically enable unparalleled stability. This work provides new guidance for the rational design of ultradurable harsh‐condition operation catalysts for industrial catalysis.