Abstract

In photocatalysis, the resulted heat by the relaxation of most of incident light no longer acts as the industrially favorite driving force back to the target photo‐reaction due to more or less the negative relation between photocatalytic efficiency and temperature. Here, we reported a visible light‐sensitized protocol that completely reversed the negatively temperature‐dependent efficiency in photo‐driven CO2 methanation with saturated water vapor. Uniform Pt/N‐TiO2/PDI self‐assembly material decisively injects the excited electron of PDI sensitizer into N‐TiO2 forming Ti‐H hydride which is crucially temperature‐dependent nucleophilic species to dominate CO2 methanation, rather than conventionally separated and trapped electrons on the conductor band. Meanwhile, the ternary composite lifts itself temperature from room temperature to 305.2 °C within 400s only by the failure excitation upon simulated sunlight of 2.5 W/cm2, and smoothly achieves CO2 methanation with a record number of 4.98 mmol g‐1 h‐1 rate, compared to less than 0.02 mmol g‐1 h‐1 at classic Pt/N‐TiO2/UV photocatalysis without PDI sensitization. This approach can reuse ~53.9% of the relaxed heat energy from the incident light thereby allow high‐intensity incident light as strong as possible within a flowing photo‐reactor, opening the most likely gateways to industrialization.