Dipole polarization modulating of vinylene-linked covalent organic frameworks for efficient photocatalytic hydrogen evolution

Photocatalytic hydrogen (H₂) evolution using covalent organic frameworks (COFs) is an attractive and promising avenue for exploration, but one of its big challenges is low photo-induced charge separation. In this study, we present a straightforward and facile dipole polarization engineering strategy to enhance charge separation efficiency, achieved through atomic modulation (O, S, and Se) of the COF monomer. Our findings demonstrate that incorporating atoms with varying electronegativities into the COF matrix significantly influences the local dipole moment, thereby affecting charge separation efficiency and photostability, which in turn affects the rates of photocatalytic H₂ evolution. As a result, the newly developed TMT-BO-COF, which contains highly electronegative O atoms, exhibits the lowest exciton binding energy, the highest efficiency in charge separation and transportation, and the longest lifetime of the active charges. This leads to an impressive average H₂ production rate of 23.7 mmol g⁻¹ h⁻¹, which is 2.5 and 24.5 times higher than that of TMT-BS-COF (containing S atoms) and TMT-BSe-COF (containing Se atoms), respectively. A novel photocatalytic hydrogen evolution mechanism based on proton-coupled electron transfer on N in the structure of triazine rings in vinylene-linked COFs is proposed by theoretical calculations. Our findings provide new insights into the design of highly photoactive organic framework materials for H₂ evolution and beyond.