Electronic Properties Modulation for Two-Dimensional Materials of Boron Phosphorus Monolayer And Derived Single Atom Catalysts for The Hydrogen Evolution Reaction

Abstract

Electrocatalytic hydrogen evolution reaction (HER) is the core of the future renewable energy field and an important part of clean energy technology. It is urgent to find a noble metal free catalyst with high stability, good conductivity and economic efficiency for HER. Two-dimensional (2D) materials such as hexagonal boron nitride formed by the combination of B and N atoms of group III-V elements have been substantiated with significant electronic properties while the 2D materials composed of B and P is inferior in terms of certain electronic properties. This paper reports for the first time the application of two recent 2D boron phosphorus monolayer compounds (BS-B1P1 and PH-B1P1) as excellent single-atom catalysts (SACs) for HER. We have demonstrated that boron phosphorus compounds can obviously improve its electrical conductivity through single-atom transition metal (TM) doping through the density of state (DOS) calculations, which promises their applications in HER. Hence, an electrocatalyst is computer-aided designed with isolated TM single atom of 3d, 4d, and 5d supported on BS-B1P1 and PH-B1P1 to construct SACs with excellent HER performance. Interestingly, we find that the these SACs can show high HER activity in a wide pH-range. Among all SACs studied, Co-, Cr-, Ti-, Nb-, Ag-,and Hf-embedded BS-B1P1 have excellent catalytic activity in acidic conditions while Ta-, Re-, Os-, Ir-, and Au-embedded BS-B1P1 show high catalytic activity in alkaline conditions. Mn@PH-B1P1 shows high catalytic activity only in acidic environment. Especially, Tc@BS-B1P1system exhibits promising catalytic activity, which owns high active in either acidic or alkaline conditions. Our work provides a highly active HER catalyst with pH regulation, providing a cost-effective alternative to traditional Pt-based catalysts for sustainable hydrogen extraction.

Keywords: DFT, 2D materials, Single atom catalysts, HER