Unveiling the bifunctional modulation evoked by bromine doping of CoP towards efficient hydrolytic hydrogen generation

Developing efficient and economical catalysts for hydrolytic hydrogen production from chemical hydrogen storage materials such as ammonia borane and NaBH4 is highly desirable but challenging. Herein, Br doped CoP nanoparticles in a carbon-based polyhedron with controllable morphology were developed as such an efficient hydrogen generation catalyst, and the bifunctional modulation of Br doping was explored. Firstly, regulating the doping content of Br results in the formation of more and larger nanopores in the CoP polyhedron, exposing more accessible active sites. Secondly, Co vacancies are introduced via Br doping, which significantly optimizes the electronic structure of Co atom, thus boosting AB and water dissociation, i.e., the rate-determining step (RDS). Therefore, the Br1-CoP@C catalyst with optimal composition exhibited a superb turnover frequency (TOF) of 67.3 min-1, implying an astonishing over 3-fold improvement compared with CoP@C. These findings showcase a novel and promising approach to build high-efficiency nanocatalysts for hydrogen production and beyond.