In the photothermal synergistic catalytic conversion of CO₂ and H₂O, the catalyst harnesses solar energy to accumulate heat, thereby elevating the reaction system’s temperature. The influence of this temperature effect on surface chemical reactions remains an underexplored area. Here the impact of temperature on the surface-level thermodynamic reactions and conversion of CO₂ with H₂O on oxide semiconductors at the atomic scale was investigated using first-principle calculations. 13 different metal oxides and 5 transition metal clusters were used to introduce surface functional sites on the TiO₂ supporting catalyst. The potential metal oxide cocatalysts that could be most beneficial to the following conversion of CO₂ by H₂O were initially screened by calculating the degrees of promotion of CO₂ adsorption and activation of surface H to provide protons. The proton donation and hydrogen evolution difficulty from H₂O were further analyzed, identifying transition metal cocatalysts that promote direct CO₂ hydrogenation. Upon introducing bifunctional sites to facilitate adsorption and reduction, the production of CH₃OH and CH₄ could be further enhanced through the facilitation of the proton donation process of H₂O. The results of Gibbs free-energy calculations revealed that increasing temperature enhances the reaction thermodynamics for each C1 product formation at different surface sites to varying degrees. These findings offer valuable theoretical insights for designing and regulating active sites on oxide semiconductor surfaces for efficient photothermal catalytic CO₂ reduction by H₂O.

在CO ₂ 和H ₂ O的光热协同催化转化中，催化剂利用太阳能积聚热量，从而提高反应体系的温度。这种温度效应对表面化学反应的影响仍然是一个尚未充分探索的领域。这里使用第一原理计算研究了温度对表面级热力学反应以及原子尺度上氧化物半导体上 CO ₂ 与 H ₂ O 转化的影响。使用13种不同的金属氧化物和5种过渡金属簇在TiO ₂ 负载催化剂上引入表面功能位点。通过计算CO ₂ 的潜在金属氧化物助催化剂> 吸附并活化表面H以提供质子。进一步分析了 H ₂ O 的质子供给和析氢难度，确定了促进 CO ₂ 直接加氢的过渡金属助催化剂。通过引入双功能位点促进吸附和还原，可以通过促进 H ₂ 的质子捐赠过程进一步增强 CH ₃ OH 和 CH ₄ 的产生。 b12> O。吉布斯自由能计算结果表明，升高温度不同程度地增强了不同表面位点各C1产物形成的反应热力学。这些发现为设计和调节氧化物半导体表面的活性位点以通过 H ₂ O 有效光热催化 CO ₂ 还原提供了宝贵的理论见解。