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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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图 1 GGA-PBE泛函计算得到的单层FRP的 (a)优化结构俯视图和侧视图, 其中数字1—6表示H吸附顶位, 7表示H吸附的空心位, 8和9为H吸附的桥位; (b)能带结构和态密度; (c)析氢反应的吉布斯自由能图; (d)第一布里渊为区
Figure 1. (a) Top and side views of the optimized structure, where the numbers 1–6 represent the top sites for hydrogen adsorption, 7 represents the hollow site for hydrogen adsorption, and 8 and 9 are the bridge sites for hydrogen adsorption; (b) band structure and density of states; (c) Gibbs free energy illustration of hydrogen evolution reaction (HER); (d) the first Brillouin zone of FRP monolayer at the GGA-PBE level.
图 2 GGA-PBE泛函计算得到的X掺杂单层FRP的(a)缺陷形成能和(b)氢吸附能
Figure 2. At the GGA-PBE level, the calculated (a) defect formation energies and (b) hydrogen adsorption energies of X-doped FRP monolayer.
图 3 GGA-PBE泛函计算得到的掺杂体系在不同掺杂位点下的ΔGH*计算结果 (a)位点1; (b)位点2; (c)位点3; (d)位点4; (e)位点5; (f)位点6
Figure 3. At the GGA-PBE level, the calculated H adsorption Gibbs free energy ΔGH* of the doped systems on doping: (a) Site 1; (b) site 2; (c) site 3; (d) site 4; (e) site 5; (f) site 6.
图 4 GGA-PBE泛函计算得到的掺杂体系在不同掺杂位点下的ΔGH* 与X pz带中心的相关性 (a)位点1; (b)位点2; (c)位点3; (d)位点4; (e)位点5; (f)位点6
Figure 4. At the GGA-PBE level, the ΔGH* as a function of the X pz band center at doping: (a) Site 1; (b) site 2; (c) site 3; (d) site 4; (e) site 5; (f) site 6.
图 5 GGA-PBE泛函计算得到的掺杂体系在位点1下的投影能带结构图 (a) B掺杂; (b) N掺杂; (c) O掺杂; (d) S掺杂; (e) As掺杂; (f) Se掺杂, 其中蓝色方形的大小代表X p轨道的权重
Figure 5. At the GGA-PBE level, orbital-resolved energy band structures of the doped systems at site 1: (a) B doping; (b) N doping; (c) O doping; (d) S doping; (e) As doping; (f) Se doping, the size of the blue square represents the weight of the X p orbital projection.
图 6 GGA-PBE泛函计算得到的掺杂体系在位点1下的态密度图 (a) B掺杂; (b) N掺杂; (c) O掺杂; (d) S掺杂; (e) As掺杂; (f) Se掺杂
Figure 6. At the GGA-PBE level, the density of states of the doped systems for doped system at site 1: (a) B doping; (b) N doping; (c) O doping; (d) S doping; (e) As doping; (d) Se doping.
图 7 GGA-PBE泛函计算得到的氢吸附于活性位点1时掺杂体系的投影态密度图
Figure 7. At the GGA-PBE level, the projected DOS of an H atom adsorbed on the active site 1 of the doped systems.
图 8 (a) GGA-PBE泛函计算得到的氢分别吸附于活性位点3、位点2和位点6时掺杂体系的投影态密度图; (b) 掺杂体系与吸附物H(Ads)之间成键的示意图
Figure 8. (a) At the GGA-PBE level, the projected DOS of an H atom adsorbed on the active site 3, site 2, and site 6 of the doped systems; (b) schematic illustration of bond formation between the doped systems and the adsorbate (Ads).
图 9 GGA-PBE泛函计算得到的过电位随ΔGH*变化的火山曲线图, 插图为–0.25—0.25 eV区间内过电势与ΔGH*关系放大图
Figure 9. At the GGA-PBE level, the volcano curves of overpotential as functions of ΔGH* for all the doped systems, the inset represents the magnification of overpotential as functions of ΔGH* in the range of –0.25–0.25 eV.
图 10 HSE06杂化泛函计算得到的火山顶四种掺杂体系与单层磷烯(FRP, VP[57]和BP[58])、单层二硫化物(SnS2[57]和MoS2[59])、单层g-C3N4[60]及BiVO4(001)[58]表面的导带和价带的带边位置与水分解氧化还原电位的相对关系, 图中灰色区域表示杂质带.
Figure 10. At HSE06 level, the conduction and valence band edge positions and the redox potential of water splitting of the four doped systems at the volcano peak, single-layer phosphorene (FRP, VP[57], and BP[58]), single-layer disulfides (SnS2[57] and MoS2[59]), single-layer g-C3N4[60], and BiVO4 (001)[58] surface. The gray area represents the impurity band.
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