Localization of Photothermal Effect Enables Impetus Transition from Heating to Solar Energy for Liquid‐Phase Reaction with Superior Productivity

Abstract Thermally driven reactions are fundamental but energy‐intensive for chemical production. Solar‐induced photothermal effect is anticipated to thoroughly substitute bulk heating as sustainable power for liquid‐phase reactions, but this impetus transition has not been achieved due to the undesired dissipation of photothermal energy to solvent. Here, we propose a novel photothermal catalyst architecture (ZrCP/CNT) by coating photothermal core with low‐thermal‐conductivity active layer that serves as both catalytic center and heat insulation fence to enable photothermal catalytic transfer hydrogenation of furfural to furfuryl alcohol. Owing to the leveraging of solar energy, ZrCP/CNT delivers specific productivity of 57.1 mmol g −1 h −1 , surpassing the state‐of‐the‐art catalysts regardless of reaction conditions. The superior performance is attributed to the localized high‐temperature gradient resulted from the in situ concentration of photothermal energy in active layer. The strategy also works for other aldehydes and variational illumination. These findings will guide general photothermal system design for extensive liquid‐phase reactions.