Exploration of hydrogen evolution reaction (HER) by using first row transition metals doped B6 complexes as support materials

Production of clean hydrogen fuel (H₂) has gained a significant importance nowadays through hydrogen evolution reaction (HER). However, a crucial requirement of HER is a low cost but an efficient catalyst. Single-atom catalysis has emerged as a promising strategy to meet this demand. In this study, we investigated late first row transition metals adsorbed six-membered boron rings (TM-B6; TM = Co, Cu, Zn, Ni, Fe) as potential single-atom catalysts for HER, aiming to identify less expensive electrocatalysts with high efficiency. Our findings demonstrate that complex reactions are thermodynamically favorable, highlighting their synthetic applicability. All transition metal doped B6 complexes have adsorption energies of −1.08 to −3.54 eV. Natural bond orbital (NBO) analysis indicated the charge transfer from transition metals to the boron ring, and then to hydrogen upon adsorption. HOMO-LUMO energy gaps of transition metal-adsorbed boron complexes range from 3.15 to 5.19 eV, and changed after hydrogen adsorption, confirming electronic stability. Molecular dynamic (MD) analysis elucidated the high stability of the pure and doped complexes at very high temperature. Noncovalent interactions and density of states analyses further confirm the potential of transition metal-adsorbed boron complexes as a supportive surface for HER.