Synergistic Modulation between Non-thermal and Thermal Effects in Photothermal Catalysis based on Modified In₂O₃

To promote the solar-energy cascadeutilization, it is necessaryto increase the thermal effect of irradiation in the catalytic reactions,while simultaneously augmenting the non-thermal effect, so as to fulfillphotothermal coupling. Herein, the non-thermal and thermal effectof light radiation on the surface of In2O3-basedcatalysts are explored and enhanced by the modification of transitionmetals Fe and Cu. Optical characterizations combined with water-splittingexperiments show that Fe doping greatly broadens the radiation responserange and enhances the absorption intensity of semiconductors'intrinsic portion, and Cu doping facilitates the absorption of visible-infraredlight. The concurrent incorporation of Fe and Cu offers synergisticbenefits, resulting in improved radiation response range, carrierseparation and migration, as well as higher photothermal temperatureupon photoexcitation. Collectively, these advantages comprehensivelyenhance the photothermal synergistic water-splitting reactivity. Thecharacterizations under variable temperature conditions have demonstratedthat the reaction temperature exerts a significant influence on theprocess of radiation absorption and conversion, ultimately impactingthe non-thermal effect. The results of DFT calculations have revealedthat the increasing temperature directly impacts the chemical reactionby reducing the energy barrier associated with the rate-determiningstep. These findings shine new light on the fundamental mechanismsunderlying non-thermal and thermal effect, while also imparting significantinsights for photo-thermal-coupled catalyst designing.