Surface functionalization of phosphorene via P-H bond for ambient protection and robust photocatalytic H2 evolution

• Published in: Science China materials 2022-05, Vol.65 (5), p.1245-1251
• Main Authors: Shi, Rui, Kang, Lei, Bai, Xiaojuan, Chen, Yong
• Format: Article
• Language: English
• Subjects: Atomic properties; Chemical bonds; Chemistry and Materials Science; Chemistry/Food Science; Covalence; Covalent bonds; Density functional theory; Hydrogen bonds; Hydrogen evolution; Hydrogenation; Materials Science; Oxidation; Phosphorene; Phosphorus; Photocatalysis; Solar energy conversion
• ISSN: 2095-8226; 2199-4501
• DOI: 10.1007/s40843-021-1843-y

The facile oxidation of few-layer black phosphorus (i.e., phosphorene) in the atmospheric environment is a major hurdle for its applications in photocatalytic solar-energy conversion. The introduction of protective layers, such as a surface capping layer, surface coordination, and P-C covalent functionalization, can protect phosphorene from oxidative degradation but inevitably decreases its photocatalytic performance due to the blockage of catalytic active sites. Herein, we develop a hydrogenation approach via the introduction of P-H covalent bonds on the surface of phosphorene (i.e., phosphorene-H) to inhibit the oxidation of phosphorene-H without sacrificing the original photocatalytic H 2 evolution performance. Experiments and density functional theory calculations demonstrate that about 5 mol% of phosphorus atoms in phosphorene-H are involved in forming P-H covalent bonds, hindering the reaction between O 2 and phosphorene-H in terms of thermodynamics and kinetics. This hydrogenation strategy is envisaged to augment the prospect of phosphorene in the field of photocatalysis.