Superlattice Architectures for Advancing Photothermal Catalysis: Mechanisms and Applications

ABSTRACT Photothermal catalysis has emerged as a powerful strategy to complement photocatalysis by harnessing full‐spectrum sunlight for the production of solar fuels and chemical upgrading. Despite its promise, practical implementation remains limited by inefficient management of light‐to‐electron/heat conversion and unclear catalytic mechanisms. Superlattice materials, featuring periodic structural order across atomic to macroscopic scales, offer tuneable sized crystals, controllable electronic structures, and unique catalytic functionalities. These attributes enable enhanced light capture, energy conversion, and highly efficient catalytic kinetics for photothermal catalysis. This review provides an overview of superlattice architectures in photothermal catalysis, with a systematic review of the mechanism at both atomic and macroscopic scales. Emphasis is placed on the mechanism of superlattice engineering in regulating key photothermal processes, including photo‐electron–phonon coupling and multi‐energy‐carrier dynamics. Advanced microscopic and operando characterization techniques are highlighted to elucidate reaction pathways and disentangle photothermal and photoelectrochemical contributions. Representative photothermal reactions are discussed to demonstrate how superlattice nanostructures enhance reactivity, selectivity, and product upgrading. Finally, challenges and future opportunities are outlined. This work aims to advance photothermal catalysis by introducing ultra‐fast, directional photon–electron–phonon transport channels and tailoring highly ordered surfaces and interfaces to steer solar‐driven catalysis toward more efficient, selective, and value‐oriented chemical transformations.