Isomeric linker-regulated pore curvature enables dimensional hybridization of covalent organic frameworks for efficient electrocatalytic H2O2 synthesis

Isomer-regulated curvature in reticular chemistry enables frameworks with identical chemical compositions to form 1D, 2D, or 3D architectures. These topological variants are critical in framework isomerism research, yet fundamental insights into how pore curvature impacts electrochemical performance are lacking. Herein, we synthesized curve-mediated covalent organic frameworks (COFs) with 1D/2D hybrid architectures for the high-performance electrocatalytic production of H 2 O 2 . Using solvent-controlled polymerization of positional isomers, we constructed 1D and 2D COFs with tunable dimensional architectures resulting from a linear-to-planar transition. Compared with pure 1D and 2D model COFs ( m -1DCOF and p -2DCOF ), 1D/2D framework-hybrid COFs ( mp -1DCOF and pm -2DCOF ) with curved channels and locally asymmetric electronic structures exhibit superior performance in optimizing intrinsic electrode surface reactions and mass transport processes. Remarkably, the m -phenyl-inserted pm -2DCOF with a large pore curvature regulates the adsorption mode of OOH* intermediates, reducing the energy barrier and thereby offering a kinetically advantageous reaction pathway; this COF achieves an exceptional productivity of 13.40 mol h −1 and a 2e − selectivity of 95.10%, ultimately leading to improved catalytic activity for electrocatalytic reactions.