Ag掺杂对铁酸铋系化合物光催化性能的影响

doi:10.6023/A24120364

摘要/Abstract

铁酸铋系化合物BiFeO₃和Bi₂Fe₄O₉因其结构和稳定性优势成为光催化材料的研究热点. 本工作采用溶胶-凝胶法制备了Ag掺杂BiFeO₃和Bi₂Fe₄O₉粉末, 研究了其在紫外光下对罗丹明B (RhB)溶液的光催化降解性能. 结果表明, 适量掺杂Ag (3 mol%)的Bi₂Fe₄O₉显示出优异的光催化性能, 对RhB的降解率高达96%. 然而, 对BiFeO₃而言, 掺杂Ag元素后会出现杂相Bi₂Fe₄O₉和Bi₂₅FeO₄₀, 样品的光催化性能未表现出显著提升, 其降解率仅为50%. 通过紫外-可见漫反射光谱分析发现, Bi₂Fe₄O₉具有双带隙特征, 分别为1.28 eV和1.36 eV. 结合密度泛函理论(DFT)计算得知, Ag 4d轨道在Bi₂Fe₄O₉的价带顶附近引入了缺陷能级, 有效缩小了带隙, 从而显著提高了光催化效率. 荧光光谱数据也进一步证明, Ag掺杂有效抑制了光生载流子的复合, 提高了光催化性能. 本研究为铁酸铋系化合物在光催化领域的应用与开发提供了一条可行的技术路径.

关键词: 铁酸铋, 光催化, 掺杂, 第一性原理, 缺陷能级

Bismuth ferrite-based compounds, such as BiFeO₃ and Bi₂Fe₄O₉, have attracted significant attention as photocatalytic materials due to their favorable structural properties and stability. In this study, Ag-doped BiFeO₃ and Bi₂Fe₄O₉ powders were synthesized using the sol-gel method, and their photocatalytic properties were evaluated through the degradation of Rhodamine B (RhB) under ultraviolet (UV) light. The results showed that Ag doping notably enhanced the photocatalytic properties of Bi₂Fe₄O₉. Specifically, 3 mol% Ag-doped Bi₂Fe₄O₉ exhibited an impressive RhB degradation rate of 96%, indicating its high efficiency for photocatalytic applications. In contrast, Ag doping in BiFeO₃ led to the formation of mixed phases, including Bi₂Fe₄O₉ and Bi₂₅FeO₄₀, and resulted in only a modest improvement in photocatalytic performance, with a RhB degradation rate of 50%. These findings highlight the superior photocatalytic activity of Bi₂Fe₄O₉ compared to BiFeO₃, emphasizing the importance of material composition and doping concentration in optimizing photocatalytic efficiency. Moreover, UV-Vis diffuse reflectance spectroscopy was used to investigate the electronic properties of the materials. The analysis revealed that Bi₂Fe₄O₉ exhibits a dual-bandgap feature with values of 1.28 eV and 1.36 eV, which enhances the material's ability to absorb visible light and improves its photocatalytic performance under ambient light conditions. To explore the mechanisms behind these improvements, density functional theory (DFT) calculations were conducted. The results indicate that the Ag 4d orbitals introduce defect energy levels near the valence band maximum of Bi₂Fe₄O₉, effectively narrowing the bandgap. This facilitates more efficient charge separation, which is crucial for enhancing photocatalytic properties. Fluorescence spectroscopy further confirmed that Ag doping effectively inhibits the recombination of photogenerated electron-hole pairs, further boosting the photocatalytic efficiency of Bi₂Fe₄O₉. This study provides valuable insights into the potential of Ag-doped bismuth ferrite-based compounds for advanced photocatalysis, and pave the way for the development of efficient photocatalysts for environmental and energy-related applications, such as water purification and solar energy conversion.

Key words: Bismuth ferrite, photocatalysis, doping, first-principles, defect energy levels

引用此文

胡国伟, 王晓欢, 原志鹏, 新巴雅尔, 乌力吉贺希格. Ag掺杂对铁酸铋系化合物光催化性能的影响[J]. 化学学报, 2025, 83(3): 229-236.

Guowei Hu, Xiaohuan Wang, Zhipeng Yuan, Yaer Xinba, Hexige Wuliji. Effect of Ag Doping on the Photocatalytic Performance of Bismuth Ferrite-based Compounds[J]. Acta Chimica Sinica, 2025, 83(3): 229-236.

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图/表 7

图1. (a)不同光催化剂的禁带宽度(Eg); (b) Ag元素掺杂Bi2Fe4O9光催化剂的光催化机理图(D代表缺陷能级)

Figure 1. (a) Bandgap energies of different photocatalysts; (b) Schematic illustration of the photocatalytic mechanism of Ag-doped Bi2Fe4O9 photocatalyst (D represents defect levels)

图2. (a) Bi1-xAgxFeO3 (x=0.00、0.01、0.03、0.05、0.10、0.15)样品的XRD图谱; (b) 2θ在31.6°~32.6°范围内的XRD图谱; (c) 重复实验下的BiFeO3和Bi0.99Ag0.01FeO3的XRD图谱; (d) Bi1-xAgxFeO3光催化剂对RhB的降解率

Figure 2. (a) XRD patterns of Bi1-xAgxFeO3 (x=0.00, 0.01, 0.03, 0.05, 0.10, 0.15) samples sintered at 650 ℃; (b) Enlarged XRD patterns in the 2θ range of 31.6°~32.6°; (c) XRD patterns of BiFeO3 and Bi0.99Ag0.01FeO3 under repeated experiments; (d) Degradation efficiency of RhB by Bi1-xAgxFeO3 photocatalysts

图3. (a)不同烧结温度下Bi2Fe4O9样品的XRD图谱; 烧结温度750 ℃下Bi2Fe4O9样品的(b) DSC-TG曲线和(c, d) SEM图

Figure 3. (a) XRD patterns of Bi2Fe4O9 samples sintered at different temperatures; (b) DSC-TG curve and (c, d) SEM images of Bi2Fe4O9 samples at 750 ℃

图4. (a) Bi2-xAgxFe4O9 (x=0.00、0.02、0.06、0.10、0.20、0.30)样品的XRD图谱; (b) 2θ在27.8°~28.8°范围内的XRD图谱; (c) Bi1.98Ag0.02Fe4O9样品的SEM图像; (d) Bi1.94Ag0.06Fe4O9样品的SEM图像

Figure 4. (a) XRD patterns of Bi2-xAgxFe4O9 (x=0.00, 0.02, 0.06, 0.10, 0.20, 0.30) samples; (b) Enlarged XRD patterns in the range of 2θ=27.8°~28.8°; (c) SEM image of Bi1.98Ag0.02Fe4O9 sample; (d) SEM image of Bi1.94Ag0.06Fe4O9 sample

图5. (a) Bi2-xAgxFe4O9光催化剂对RhB的光催化降解率; (b)光源照射90 min后, 不同光催化剂对RhB的降解率比较(粉色代表本工作)

Figure 5. (a) Photocatalytic degradation rate of Rhodamine B by Bi2-xAgxFe4O9 photocatalysts; (b) Comparison of degradation rates of RhB by various reported photocatalysts after 90 min of illumination from different light sources (pink represents this work)

图6. Bi2Fe4O9及Ag元素掺杂的(a, b) UV-vis漫反射吸收光谱及对应的(αhν)1/2-hν图; (c, d)电子能带结构示意图; (e, f) PDOS图

Figure 6. (a, b) UV-vis diffuse reflectance spectra and corresponding (αhν)1/2-hν plots for Bi2Fe4O9 and Ag-doped samples; (c, d) Schematic diagrams of electronic band structures; (e, f) Projected density of states (PDOS) plots

图7. BiFeO3, Bi2Fe4O9和Bi1.94Ag0.06Fe4O9样品的荧光光谱

Figure 7. PL spectra of BiFeO3, Bi2Fe4O9 and Bi1.94Ag0.06Fe4O9

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