Atomic-scale interface engineering in photocatalysis

Interfaces are central to photocatalytic solar-to-chemical conversion. Conventional heterointerfaces mainly optimize band alignment and macroscopic charge separation. Atomic-scale interface engineering in photocatalysis denotes the strategic construction of atomically precise interfacial architectures with controlled chemical bonding, lattice coherence, and coordination environments, thereby governing interfacial charge redistribution, carrier routing, and reaction intermediate activation at atom level. In this review, we highlight advanced synthetic approaches-including seed-mediated growth, cation exchange, and coordination-confined anchoring-and discuss how operando spectroscopy combined with density functional theory elucidates interfacial electric fields and orbital coupling in steering multi-electron reactions such as CO₂ reduction and H₂ evolution. We further systematically summarize the design principles and the recent development of covalently bridged ensembles, epitaxial heterointerfaces, defect-mediated boundaries, and atomically dispersed single/dual-atom sites. Finally, emerging directions in superlattice engineering and dipole-induced polarization are outlined to guide the rational development of next-generation photocatalysts with enhanced quantum efficiency and product selectivity.