The Linkage‐Moderated Covalent Organic Frameworks with C=N and NN on Charge Transfer Kinetics Towards the Robust Photocatalytic Hydrogen Activity

Since the linkages structured in covalent organic frameworks (COFs) usually impact the charge transfer behavior during photocatalytic hydrogen evolution reaction (pc-HER), linkage dependence on charge transfer kinetics should be further claimed. Herein, COFs with N-based linkages and pyrene-based building nodes are constructed to enable us to obtain new clues about the charge transfer behavior and evolution tendency relevant to linkages at a molecular level for pc-HER. It is demonstrated that photo-excited electrons preferably move to the N sites in C=N linkage for pc-HER and are trapped around NN linkage as well. A high electron transfer rate does not point to high photocatalytic activity directly, while a small difference between the electron transfer rate and electron recombination rate ΔkCT - CR predicts the inefficiency of charge transfer in Azod-COFs. Contrarily, large value of ΔkCT - CR in the case of Benzd-COFs, demonstrats an unimpeded charge transfer process to result in boosted pc-HER rate (2027.3 µmol h-1 g-1 ). This work offers a prominent strategy for the reasonable design of efficient photocatalysts at the molecular level for structural regulation and achieves an efficient charge transfer process for the pc-HER process.