Topology Control of Covalent Organic Frameworks with Interlaced Unsaturated 2D and Saturated 3D Units for Boosting Electrocatalytic Hydrogen Peroxide Production

Modulating the electronic state of multicomponent covalent organic framework (COF) electrocatalysts is crucial for enhancing catalytic activity. However, the effect of dimensionality on their physicochemical functionalities is still lacking. Herein, we report an interlaced unsaturated 2D and saturated 3D strategy to develop multicomponent‐regulated COFs with tunable gradient dimensionality for high selectivity and activity electrocatalysis. Compared with the two‐component 2D and 3D model COFs, the 2D/3D framework interlaced COFs with locally irregular dimensions and electronic structures are more practical in optimizing the intrinsic electrode surface reaction and mass transfer. Remarkably, the unsaturated 2D‐inserted 3D TAE‐COF regulates the adsorption mode of OOH* species to supply a favorable dynamic pathway for the H2O2 process, thereby achieving an excellent production rate of 8.50 mol gcat−1 h−1. Moreover, utilizing theoretical calculation and in situ ATR‐FTIR experiment, we found that the central carbon atom of the tetraphenyl‐based unit (site‐1 and site‐6) are potential active sites. This strategy of operating the adsorption ability of reactants with dimensionality‐interconnected building blocks provides an idea for designing durable and efficient electrocatalysts.