Conformation‐Induced Dipole Polarization Engineering in Hierarchical Vinylene‐Linked Covalent Organic Frameworks for Enhanced Photocatalytic H ₂ O ₂ Production

Abstract Hierarchical vinylene‐linked covalent organic frameworks (COFs) are gaining recognition as highly promising materials for various applications, owing to their exceptional stability, efficient electronic transfer capability and intrinsic hierarchical porosity. However, designing and constructing hierarchical vinylene‐linked COFs with adaptable electronic structures remains a nascent and challenging field. Herein, two hierarchical vinylene‐linked COFs ( SM‐PT and AM‐PT ) with symmetrical and asymmetrical conformations, respectively, were successfully constructed from two innovative pyrimidine‐based monomers through an asymmetric conformation strategy. Specially, the conformation modulation allows directional control over the local electronic structures of thes COFs. As a result, AM‐PT with an asymmetric conformation demonstrates improved dipole polarization, greatly facilitating the exciton dissociation and charge transfer, which leads to remarkable efficiency in the photocatalytic H ₂ O ₂ production, exceedingly outperforming its symmetric counterpart SM‐PT . Consequently, AM‐PT achieved remarkable photocatalytic H ₂ O ₂ production rates of 5936 µmol g ⁻¹ h−1 in pure water and 11427 µmol g ⁻¹ h ⁻¹ with benzyl alcohol as a hole sacrificial agent. Remarkably, AM‐PT achieves high H ₂ O ₂ concentrations and robust photocatalytic degradation activity toward environmental pollutants in a continuous‐flow system, underscoring its considerable promise for future industrial applications.