Unlocking the non-covalent electrostatic engineering of photocatalysts: from molecular interactions to multifield tuning strategies toward enhanced charge dynamics

Photocatalysis is one of the most capable green energy techniques for sustainable solar-to-chemical energy conversion. However, the speedy recombination of photocarriers remains a critical bottleneck in achieving high photocatalytic efficiency. Recent advancements have underscored the pivotal role of internal and external electrostatic fields in regulating charge dynamics within semiconductor systems. This review highlights the emerging strategy of employing non-covalent electrostatic interactions to modulate photocatalytic behavior. Internally, spontaneous polarization within polar or ferroelectric semiconductors facilitates efficient charge separation through built-in electric fields. Externally applied mechanical stress and magnetic fields further augment these effects via piezoelectric and magnetoelectric phenomena, offering dynamic control over carrier transport. Beyond macroscopic fields, subtle non-covalent electrostatic forces, such as hydrogen bonds, van der Waals forces, and π-π stacking, significantly influence surface adsorption, electronic structure modulation, and interfacial charge transfer processes. Combining these external influences with semiconductor properties, we can develop innovative strategies to stabilize the reactive intermediates and reduce the recombination pathways, improving the practical implications of these synergistic effects in energy conversion and environmental remediation. This review systematically elucidates the mechanistic contributions of internal polarization and external fields to the modulation of non-covalent electrostatic forces in photocatalytic systems. Emphasis is placed on material design strategies that integrate structural polarity, field-responsive behavior, and interfacial engineering to achieve superior photocatalytic performance. Finally, the prospects of non-covalent electrostatic interactions in photocatalysis are discussed, providing insights to guide the rational development of more efficient and sustainable photocatalytic systems.