Photothermal effect promoting the reconstruction and mass-energy transfer for the enhancement of three-dimensional confinement catalysis

Photothermal catalysis, as an emerging technology, has attracted much attention owing to its high efficiency and excellent sustainability. Current industrial processes integrating solar energy with fossil fuels for large-scale chemical production remain hindered by several challenges, including dynamic catalytic site restructuring that alters product selectivity and progressive catalyst deactivation that compromises economic viability. Therefore, a reasonable structural design could enormously enhance the mass and energy transfer during catalytic reactions. Considering the complexity of the reaction micro-environment, catalytic site reconstruction plays a crucial role in dynamic photothermal catalysis. Taking into account the spatial and temporal reaction processes, this review is focused on the latest progress of the catalytic sites confined to different three-dimensional (3D) structures. Initially, we provide an introduction to the mechanism of photothermal reaction on 3D structures, focusing on the mass and energy transferring pathways and the corresponding reactions. Subsequently, several typical distribution types of the catalytic sites are discussed, emphasizing that various 3D configurations modified with different types of catalytic sites would drive different reactions, including the biological enzyme site interaction process. We further elucidate the dynamic reconstruction of active sites under varying microenvironmental conditions, primarily induced by small-molecule adsorption and weak interfacial fields. Moreover, the applications of photothermal 3D materials are discussed under realistic reaction conditions, opening a new window for filling the gap between micro-structure and macro-process in catalysis. Finally, we briefly summarized the future challenges in solar-assisted catalytic engineering.