Silicon and Phosphorus Co-doped Bipyridine-Linked Covalent Triazine Framework as a Promising Metal-Free Catalyst for Hydrogen Evolution Reaction: A Theoretical Investigation.

Electrocatalytic water spliting is the most attractive route for hydrogen production, but the development of nonprecious, stable, and high-performance catalysts for hydrogen evolution reaction (HER) to replace the scarce platinum group metal-based electrocatalysts is still a challenging task for the scientific community. In this work, within the framework of density functional theory computations, we have predicted that a silicon and phosphorus co-doped bipyridine-linked covalent triazine framework, followed by substitution of bipyridine hydrogens at the P-site with fluorine atoms, may be a potential catalyst for HER. Our predicted model system (SiPF-Bpy-CTF) exhibits a very low band gap (7 meV), which may exhibit facile charge transfer kinetics during HER. Using the Gibbs free energy for the adsorption of atomic hydrogen ([Formula: see text]) as the key descriptor, we have found that our proposed model system (SiPF-Bpy-CTF) exhibits superior HER catalytic activity, with its [Formula: see text] being close to the ideal value (0 eV).