铋氧双空位的超薄钒酸铋的构建及其光催化氮气还原

doi:10.1016/S1872-2067(25)64808-X

摘要/Abstract

摘要：

氨(NH₃)作为一种重要的化学品和潜在的清洁能源载体, 广泛应用于制药、能源和纺织等领域. 传统合成方法存在能耗高、碳排放高等问题. 光催化固氮技术以其绿色、可持续等特点受到广泛关注, 但面临光生载流子复合率高、反应活性位点不足等挑战, 这在很大程度上限制了光催化固氮的效率. 本研究制备了具有双空位的超薄钒酸铋光催化剂, 通过形貌调控和空位工程有效地解决了上述问题. 超薄结构不仅能富集光生电子, 而且可以增加活性位点与N₂/H₂O的接触; 同时, 空位工程可以增强催化剂对N₂/H₂O的吸附和活化能力, 二者共同作用, 促进了NH₃的生成. 因此, 利用双空位和超薄结构的协同作用以实现高效的氨产率是本文的主要研究思路.

本文通过溶剂热法和离子共晶溶剂法协同处理构筑了含铋和氧双空位的超薄钒酸铋纳米片(2D-V_Bi+O-BVO), 并将其用于光催化氮气还原反应. 扫描电子显微镜、透射电子显微镜(TEM)和原子力显微镜的表征结果表明, BiVO₄的厚度经两步法改性后显著降低, 从初始的1200 nm锐减至15 nm, 实现了材料的超薄化. 超薄结构不仅增加了活性位点的接触, 而且缩短了光生载流子的迁移距离. 此外, 光沉积实验结果表明, (040)是电子的活性晶面. 超薄结构还可以最大化地暴露该晶面, 有利于高效富集光生电子. 结合TEM、X射线光电子能谱和电子顺磁共振表征, 证实了BiVO₄中氧空位和铋空位的成功构建. 密度泛函理论计算结果表明, 氧空位和铋空位可以分别吸附并活化N₂和H₂O分子, 从而有效促进光催化氮气还原反应的进行. X射线光电子能价带谱和紫外光电子能谱等表征结果显示, 双空位和超薄结构协同调整了BiVO₄的能带结构, 使其具有更强的还原能力. 光电流响应、电化学阻抗谱、光致发光光谱和时间分辨光致发光光谱的表征结果表明, 双空位和超薄结构协同增强了BiVO₄的光生载流子寿命, 提高了光生载流子的分离速率, 从而提高BiVO₄的光催化能力. 此外, 原位红外光谱的表征结果表明, N₂可以在BiVO₄上被有效吸附并活化. NH₂-NH₂活性物种的存在证明其通过交替结合路径进行反应. 得益于双空位和超薄结构的协同作用, 2D-V_Bi+O-BVO在模拟太阳光照射下表现出最优的光催化固氮性能: 氨产率高达158.73 μmol·g^-1·h^-1, 是bulk-BMO的4.7倍. 循环实验和反应后的一系列表征结果显示, 2D-V_Bi+O-BVO具有优异的稳定性.

综上, 双空位和超薄结构的的协同构建有效提高了BiVO₄的光催化固氮性能. 本研究为通过协同双空位和超薄结构的高效固氮催化剂合成提供新的见解和视角. 在此基础上, 未来的研究可以专注于异质结构或掺杂策略的修饰, 以扩展该领域研究的深度和广度.

关键词: 氧空位, 铋空位, 超薄结构, 光催化, 氮气还原

Abstract:

The efficient utilization of photogenerated electrons and the effective activation of reactive molecules are among the major challenges in photocatalytic nitrogen reduction. Defect engineering can enhance the catalyst's ability to adsorb and activate N₂ and H₂O, while the ultrathin structure with maximized active crystal facets can maximize the enrichment of effective photogenerated electrons. This work employs a two-step synergistic method to fabricate ultrathin BiVO₄ with oxygen vacancies and bismuth vacancies (2D-V_Bi+O-BVO, thickness < 20 nm) for photocatalytic nitrogen reduction. Scanning electron microscopy, transmission electron microscopy (TEM), and atomic force microscopy characterization confirm the transformation of BiVO₄ from bulk material (bulk-BVO, ~1300 nm) to an ultrathin structure (~15 nm). TEM, X-ray photoelectron spectroscopy, electron paramagnetic resonance characterizations, and density functional theory (DFT) calculations verify the construction of oxygen and bismuth vacancies in the ultrathin BiVO₄. Compared to bulk-BVO, the photocatalytic nitrogen fixation efficiency of 2D-V_Bi+O-BVO is increased by 4.7 times, with the highest activity reaching 158.73 μmol·g^-1·h^-1. N₂-temperature programmed desorption and DFT calculations demonstrate that the oxygen and bismuth vacancies in BiVO₄, respectively, promote the adsorption/activation of N₂ and H₂O, which is crucial for the overall nitrogen reduction reaction. Photo-deposition experiments prove that the (040) plane is the active surface for electrons. And the ultrathin structure maximizes the (040) facet of BiVO₄, which is conducive to the high enrichment of electrons. Meanwhile, more active sites can be exposed for the activation of N₂ and H₂O. In situ infrared spectroscopy confirms that N₂ can be effectively adsorbed onto 2D-V_Bi+O-BVO, and the presence of NH₂-NH₂ active species is consistent with the alternating reaction pathway. This study provides new insights into the development of green and efficient photocatalysts with dual vacancies and ultrathin structures.

Key words: Oxygen vacancies, Bismuth vacancies, Ultrathin structures, Photocatalysis, Nitrogen reduction

陈家辉, 孟跃, 谢波, 倪哲明, 夏盛杰. 铋氧双空位的超薄钒酸铋的构建及其光催化氮气还原[J]. 催化学报, 2025, 78: 265-278.

Jiahui Chen, Yue Meng, Bo Xie, Zheming Ni, Shengjie Xia. Construction of ultrathin BiVO₄ nanosheets with bismuth-oxygen dual vacancies for photocatalytic nitrogen reduction[J]. Chinese Journal of Catalysis, 2025, 78: 265-278.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(25)64808-X

https://www.cjcatal.com/CN/Y2025/V78/I11/265

图/表 8

Fig. 1. (a-d) SEM images of different samples. TEM image (e), EDS image (f), and HRTEM (g,h) images of 2D-VBi+O-BVO. (i) XRD patterns of different samples.

Fig. 2. (a-c) SEM images of different samples. (d) Schematic illustration of the ultrathin structure of BiVO4. TEM image (e), AFM image (f), height distribution image (g), and high sensor image (h) of 2D-VBi+O-BVO.

Fig. 3. HRTEM image (a), Fourier inverse transform image (b), atomic gradient image (c), and DFT models image (d) of 2D-VBi+O-BVO. (e) XPS spectra of different samples. High-resolution XPS spectra for V (f), Bi 4f (g) and O 1s (h) of different samples. (i) EPR spectra of different samples.

Table 1 Relative elemental content analysis of bulk-BVO, 2D-VO-BVO, VBi-BVO, and 2D-VBi+O-BVO.

Sample	Bi atom%	O atom %	V atom %	Bi:O:V
bulk-BVO	17.61%	71.51%	10.88%	1.6:6.6:1
2D-V_O-BVO	19.59%	69.61%	10.80%	1.8:6.4:1
V_Bi-BVO	6.64%	73.79%	19.57%	0.3:3.7:1
2D-V_Bi+O-BVO	13.85%	71.07%	15.08%	0.9:4.7:1

Fig. 4. (a) Photocatalytic nitrogen fixation activity of different samples. (b) By-products content in photocatalytic nitrogen fixation of 2D-VBi+O-BVO. (c) The NH3 yield of 2D-VBi+O-BVO under different conditions. (d) The results of 15N2 isotope labeling by NMR spectrum. (e) Photocatalytic ammonia production rates for cyclic tests of 2D-VBi+O-BVO. (f) The NH3 yield of 2D-VBi+O-BVO over time. DRS spectra and tauc plots of (αhv)1/2 versus energy (hν) (g), valence-band spectra (h), schematic diagrams (i) of the band structure for different samples.

Fig. 5. Photocurrent response curves (a) and EIS (b) of different samples. (c) PL spectra of bulk-BVO and 2D-VBi+O-BVO. (d,e) SEM image and element mapping of photo-deposited Ag on bulk-BiVO4. (f) Schematic illustration of the ultrathin structural transformation. N2 adsorption-desorption isotherm (g) and N2-TPD spectra (h) of bulk-BVO and 2D-VBi+O-BVO. (i) In-situ FTIR spectra of the N2 photoreduction reaction with 2D-VBi+O-BVO.

Fig. 6. (a-c) The in-situ FTIR spectra of the samples in different ranges as a function of time. (d,e) the distal and alternative binding pathways for the N2 reduction on 2D-VBi+O-BVO. The DFT adsorption models of N2 molecules (f,g) and H2O molecules (h,i) on bulk-BVO and 2D-VBi+O-BVO. Purple, grey, red, blue, and yellow spheres denote Bi, V, O, N, and H atoms, respectively.

Fig. 7. The photocatalytic ammonia synthesis mechanism of ultrathin BiVO4 with bismuth and oxygen dual vacancies.

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