Photocatalytic reduction of CO 2 to CH 4 on TiO 2 remains a major challenge due to the complex multiple electron-proton coupling process. Notably, photothermal catalysis by synergistically promoting photogenerated charge separation and thermodynamic modulation has emerged as a promising strategy to promote the selective CH 4 production, while the special influence of photo-to-thermal effect on such process is still indistinct. In this work, TiO 2 exhibits an outstanding CH 4 production rate of 29.79 µmol·g − 1 ·h − 1 with hugely increased CH 4 selectivity of 87.0% only rely on the optimization of reaction conditions (light intensity dominated photo-to-thermal effects). Combined in situ DRIFTS, electrochemical characterization, and DFT theoretical simulations indicate that photothermal heating not only accelerate the charge transfer but also lowers the energy barrier for CO 2 protonation, promoting formation of the multiple electron-proton coupling CH 4 . This work demonstrates that photothermal synergy not only enhances catalytic activity but also enables precise control of CH 4 product selectivity through heat-mediated modulation of intermediate transformations. These findings provide a novel strategy for the highly efficient and selective photocatalytic conversion of CO 2 to CH 4 and have positive implications for advancing sustainable carbon utilization.
Wang et al. (Mon,) studied this question.