Quantifying the role of N-position in imine-based covalent organic frameworks for photocatalytic water splitting

Abstract

Through first-principles calculations, we investigated the role of N-site positioning in 2D COFs for modulating photocatalytic water splitting. Water activation at the pyridine N-site triggers protonation, inducing a push–pull electronic interaction, lowering the OER/HER thermodynamic barriers. Furthermore, N-atom positioning significantly alters the electron density and exciton binding energy, thereby improving the reaction thermodynamics.