From Photon Capture to Barrier Crossing: The Landscape of Full‐Spectrum Photothermal Catalysis

ABSTRACT Conventional photocatalysis is constrained by narrow ultraviolet response, weak carrier driving force, and slow kinetics for high‐barrier reactions hindering efficient full‐spectrum solar utilization. Photothermal catalysis integrates photochemical effects from photogenerated carriers with photothermal conversion heat, yielding a ‘1+1>2’ synergy that offers a new route to overcome the energy bottleneck. This review focuses on full‐spectrum utilization and barrier reduction, systematically summarizing the design and conversion mechanisms of narrow‐bandgap semiconductors, plasmonic metals, carbon‐based and polymeric photothermal materials. We elucidate the multiple roles of photothermal effects, including localized thermal fields that lower apparent activation energies, hot‐electron injection that provides additional driving force, and the synergy between thermal fields and carrier dynamics that enhances charge separation. Representative applications in high‐temperature reactions, coupled water evaporation, and photo/electrocatalysis are reviewed. Finally, perspectives on mechanistic decoupling, material optimization, and practical implementation challenges are presented.