Inserted-B atoms modulating electronic structure of Pt enhancing hydrogen evolution under Universal-pH

Abstract

The development of high-performance electrocatalysts for hydrogen evolution reaction (HER) in different pH conditions is pivotal in producing green hydrogen, but remains challenging. Herein, we regulate the p-d orbitals hybridization between B and Pt for effective and durable HER at all pH ranges by controlling the inserted B atom. Consequently, the optimized B-doped Pt catalysts with 20 at.% B content (Pt80B20/C) has the highest HER performance, with only 7 mV overpotential in acidic conditions, 37 mV in alkaline media, and 47 mV in neutral media, more remarkably, have negligible attenuation during electrolysis up to 100 h, which is superior to commercial Pt/C catalysts. Theoretical calculations revealed that by inserting appropriate B atoms in the interstitial vacancies of Pt, the electronic structure of Pt is suitable for providing appropriate hydrogen intermediates (H*) adsorption/desorption strength, resulting in superior acid HER electrocatalyst performance. Besides, a strong electronic interaction existed between Pt and inserted-B atoms leaving Pt sites in an electron deficiency state, which facilitates the bond cleavage of the H-OH of H₂O, hence accelerating water dissociation and promoting neutral/alkaline HER dynamics.