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在能源危机与环境污染的双重挑战下,光催化分解水制氢技术因其绿色可持续特性成为清洁能源领域的研究热点.纤维红磷(FRP)作为一种新型准一维半导体材料,凭借其适中的带隙、高载流子迁移率及优异的空气稳定性,展现出显著的光催化析氢潜力.基于第一性原理计算,我们系统探究了一系列非金属元素X（B、C、N、O、Si、S、As和Se）掺杂对单层FRP电子结构及催化性能的调控机制.结果表明,杂质X能有效提升单层FRP的析氢反应(HER)活性.其中,四种掺杂体系（S掺杂位点1、B掺杂位点1/2/5）表现出优异的HER催化活性.尤其是B掺杂位点2体系,具有最理想的氢吸附自由能,其过电位与贵金属Pt催化剂相当.电子结构分析发现,HER催化活性的增强与吸附位点X pz带中心的下移密切相关,氢吸附自由能与X pz带中心呈现正相关性,表明X pz带中心可作为调控析氢反应活性的关键电子描述符.杂化泛函计算进一步证实,B掺杂体系的带边位置能够横跨水的氧化还原电势两侧,且光吸收范围覆盖可见光区域,表明了该体系在光催化全解水应用中的热力学可行性与光谱响应优势.该研究为基于非金属掺杂策略设计高效非金属基光催化材料提供了重要理论指导.Under the dual challenges of the energy crisis and environmental pollution, the technology of photocatalytic water splitting for hydrogen production has become a research hotspot in clean energy due to its green and sustainable characteristics. As a novel quasi-one-dimensional semiconductor material, fibrous red phosphorene (FRP) exhibits remarkable photocatalytic hydrogen evolution potential, owing to its moderate bandgap, high carrier mobility, and excellent air stability. Based on first-principles calculations, we systematically investigated the regulatory mechanisms of a series of non-metallic elements X (B, C, N, O, Si, S, As, and Se) doping on the electronic structure and catalytic performance of single-layer FRP. The results show that the element X can effectively enhance the hydrogen evolution reaction (HER) activity of single-layer FRP. Among them, four doped systems (S-doped at site 1, B-doped at sites 1/2/5) exhibit excellent catalytic activity for HER. In particular, the B-doped system at site 2 has the most ideal free energy of hydrogen adsorption (ΔGH*), and its overpotential (η = -0.074 V) is comparable to that of the noble metal Pt catalyst. Through the analysis of the electronic structure, it is found that the enhancement of the HER catalytic activity is closely related to the downward shift of the X pz-band center at the adsorption site. There is a direct proportional relationship between ΔGH* and the X pz-band center (R2 ≥ 0.78), indicating that the X pz-band center can serve as a key electronic descriptor for regulating the HER activity. Further verification by calculations using the HSE06 hybrid functional shows that the band edge positions of the B-doped system can span both sides of the redox potential of water, and the light absorption range covers the visible light region, indicating the thermodynamic feasibility and spectral response advantages of this system in the application of photocatalytic overall water splitting. This study provides important theoretical guidance for the design of efficient FRP-based photocatalytic materials based on the non-metallic doping strategy.
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Keywords:
- fibrous red phosphorene /
- doping /
- photocatalysis /
- first-principles
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