The H₂ evolution is generally considered a competing reaction in photocatalytic CO₂ reduction reaction (CO₂RR) using H₂O as the proton source. However, the reducing gas H₂ generated from H₂O splitting can be the proton source in CO₂RR under the enhanced dynamic role of the thermal effect. The reverse water gas shift (RWGS) reaction, a CO₂ hydrogenation reaction, should occur in photothermal environment owing to thermodynamically and kinetically favorable. Herein, nanostructured metal-semiconductor contact consisting of Pt nanoparticles (NPs) supported on SrTiO_3–δ nanosheets with rich oxygen vacancies (Pt-OVs-STO) was constructed for investigating its feasibility and efficiency in the RWGS reaction under photothermal effect. Our experimental results substantiate that the H₂ generated by H₂O splitting effectively contributes to the RWGS reaction over Pt-OVs-STO system. The Pt⁰ NPs not only efficiently facilitate surface charge transfer, but also lower the energy barrier of the O–H bond breaking, H₂ releasing, and RWGS reaction, thereby showing an outstanding CO₂RR performance. The strong interaction between the Pt⁰ NPs and SrTiO_3–δ has been extensively demonstrated by a series of experimental characterizations and density functional theory calculations. This work elucidates the relation between H₂ evolution and RWGS reaction over Pt⁰/SrTiO_3–δ structure in photothermal catalytic CO₂RR using H₂O as the proton source and provides new perspectives for subsequent CO₂RR.

H ₂释放通常被认为是使用H ₂ O作为质子源的光催化CO ₂还原反应(CO ₂ RR)中的竞争反应。然而，在热效应的增强动力作用下， H ₂ O裂解产生的还原气体H _{2可以成为CO 2} RR中的质子源。反向水煤气变换(RWGS) 反应是一种CO ₂加氢反应，由于热力学和动力学有利，应该在光热环境中发生。_{在此，由负载在 SrTiO 3– δ}上的 Pt 纳米粒子 (NPs) 组成的纳米结构金属-半导体接触构建了具有富氧空位的纳米片 (Pt-OVs-STO)，以研究其在光热效应下 RWGS 反应的可行性和效率。_{我们的实验结果证实，H 2} O 分裂产生的H ₂有效地促进了 Pt-OVs-STO 系统上的 RWGS 反应。Pt ^{0 NPs 不仅有效地促进了表面电荷转移，而且降低了 O-H 键断裂、H} ₂释放和 RWGS 反应的能垒，从而表现出出色的 CO ₂ RR 性能。^{Pt 0} NPs 与 SrTiO _{3– δ}之间的强相互作用已通过一系列实验表征和密度泛函理论计算得到广泛证明。该工作阐明了以H 2 O为质子源的光热催化CO 2 RR_中Pt 0 /SrTiO 3– δ结构_上^的H _2释放与RWGS反应之间的关系，并为后续的CO ₂ RR提供了新的视角。