Water splitting at imine-linked covalent organic frameworks

Covalent organic frameworks (COFs) are a promising class of metal- free catalysts, offering a high structural and functional variety. Here, we systematically study imine-linked COFs with donor (D) and ac- ceptor (A) groups using density functional theory (DFT). Using water splitting as a model reaction, we analyze the effects of protonation of the catalyst, the orientation of the imine linkage leading to differ- ent constitutional isomers, and solvation. In agreement with experi- mental results, we show that protonation decreases the band gap. In addition, COFs in which the donor is closer to the nitrogen atom of the imine group (DNCA) have lower band gaps than those in which the donor is closer to the carbon atom (DCNA). Three different D/A COFs are compared in this work, for which energies for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) and corresponding electrochemical overpotentials are computed. We show that reaction energies are very similar for DCNA and DNCA COFs. The differences in hydrogen evolution rates between the constitutional isomers observed experimentally in (photocatalytic) HER (Yang et al., Nature Commun. 13, 6317 (2022)), are proposed to be at least in part a consequence of differences in charge distribution.