新型层状BiOF光催化剂的制备及其应用研究进展

邓玉婷; 林金池; 于秀明; 朱文韬; 杨金辉; 谢水波

doi:10.13801/j.cnki.fhclxb.20240019.002

新型层状BiOF光催化剂的制备及其应用研究进展

doi: 10.13801/j.cnki.fhclxb.20240019.002

1.
南华大学　土木工程学院，衡阳 421001
2.
南华大学　污染控制与资源化技术湖南省重点实验室，衡阳 421001

基金项目: 湖南省自然科学基金(2023JJ50123)；湖南省研究生科研创新项目(CX20230974)

详细信息

通讯作者:
杨金辉，硕士，教授，硕士生导师，研究方向为水环境与水处理工程　E-mail: 842893915@qq.com

中图分类号: TQ426；TB332
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- 文章访问数: 233
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- 被引次数: 0
出版历程
- 收稿日期: 2023-11-23
- 修回日期: 2024-01-09
- 录用日期: 2024-01-12
- 网络出版日期: 2024-01-19
- 刊出日期: 2024-10-15

Advance in preparation and application of novel layered BiOF as photocatalyst

1.
School of Civil Engineering, University of South China, Hengyang 421001, China
2.
Hunan Provincial Key Laboratory of Pollution Control and Resources Technology, University of South China, Hengyang 421001, China

Funds: Hunan Provincial Natural Science Foundation (2023JJ50123); Hunan Province Graduate Research Innovation Project (CX20230974)

摘要

摘要: 世界经济迅速发展导致的环境污染和能源危机成为全球共同面对的威胁与挑战，光催化技术为该问题提供了高效的解决方案。氟氧化铋(BiOF)具有特殊的层状结构、低毒性、高稳定性、丰富的可调控性和良好的光催化性等优点，成为光催化研究领域的重要材料。然而BiOF带隙较大，导致其光生载流子易复合且电荷转移率低，因此寻求新的合成方式及改性修饰方法对提高BiOF光催化性能具有重要研究意义。本文介绍了近年来BiOF光催化剂的制备方法、改性策略、反应机制等方面的研究现状，综述分析其在降解污染物、CO₂还原、电极与电池、纳米铝热剂等环境能源领域的应用，并对该类材料未来的发展与可能面临的挑战做出展望，旨在为开发新型高效的BiOF光催化剂提供理论借鉴与技术支撑。
- 氟氧化铋 /
- 制备 /
- 改性 /
- 光催化性能 /
- 环境治理 /
- 能源转换
Abstract: The rapid development of the world economy has led to environmental pollution and energy crisis, posing a global threat and challenge. Photocatalysis technology provides an efficient solution to address these issues. Bismuth oxyfluoride (BiOF) has attracted significant attention as an important material in the field of photocatalysis due to its unique layered structure, low toxicity, high stability, tunability, and excellent photocatalytic performance. However, the wide bandgap of BiOF leads to easy recombination of photo-generated charge carriers and low charge transfer rate, thus it is of great research significance to seek new synthesis methods and modification techniques to improve the photocatalytic performance of BiOF. This paper introduces the preparation method, modification strategy and reaction mechanism in recent years. This review analyzes the applications of BiOF photocatalyst in the areas of pollutant degradation, CO₂ reduction, electrodes and batteries, and nanoaluminum thermal agents in the field of environmental energy. It also provides prospects for the future development and challenges of such materials, aiming to provide theoretical guidance and technical support for the development of novel efficient BiOF photocatalyst.
- bismuth oxyfluoride /
- preparation /
- modification /
- photocatalytic performance /
- environmental governance /
- energy conversion

HTML全文

图 1 (a) BiOF的晶体结构^[24]；(b) BiOF的带隙结构图^[25]；(c) BiOF的内部电场(IEF)示意图^[17]

Figure 1. (a) Crystal structure of BiOF^[24]; (b) Band gap structure of BiOF^[25]; (c) Internal electric field (IEF) diagram of BiOF^[17]

E—Energy; E_F—Fermi level; E_g—Band gap energy; DOS—Density of states

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图 2 BiOF的光催化机制图^[32]

Figure 2. Photocatalytic mechanism diagram of BiOF^[32]

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图 3 溶剂热法制备BiOF的过程示意图^[40]

Figure 3. Schematic diagram of the process for the preparation of BiOF using solvothermal method^[40]

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图 4 纳米棉状BiOF的TEM图像^[41]

Figure 4. TEM image of nano-cotton-like BiOF^[41]

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图 5 溶剂热法120℃ ((a)~(c))、140℃ ((d)~(f))和160℃ ((g)~(i))条件下合成的BiOF的SEM图像^[31]

Figure 5. SEM images of BiOF synthesised by solvothermal method at 120℃ ((a)-(c)), 140℃ ((d)-(f)) and 160℃ ((g)-(i))^[31]

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图 6 pH=10.7 ((a), (b))、pH=11.5 ((c), (d))、pH=11.8 ((e), (f))下BiOF的SEM和HRTEM图像；(g)生长方向由[001]到[101]的转变示意图^[44]

Figure 6. SEM and HRTEM images of BiOF at pH=10.7 ((a), (b)), pH=11.5 ((c), (d)), pH=11.8 ((e), (f)); (g) Schematic diagram of growth direction change from [001] to [101]^[44]

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图 7 球状BiOF的SEM图像^[55]

Figure 7. SEM images of spherical BiOF^[55]

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图 8 BiOCl向BiOF转换示意图^[64]

Figure 8. Schematic diagram of BiOCl to BiOF conversion^[64]

V_Eth/V_W—Ethanol/water volume ratio

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图 9 金属离子(a)和非金属元素(b)掺杂原理^[86]

Figure 9. Doping principle of metal ion (a) and non-metal element (b)^[86]

VB—Valence band; CB—Conduction band; λ—Wave length

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图 10 I型异质结(a)、II型异质结(b)、Z型异质结(c)和p-n型异质结(d)电子-空穴对分离示意图^[92]

Figure 10. Schematic illustration of separation of electron-hole pairs in the case of Type-I heterojunction (a), Type-II heterojunction (b), Z-scheme heterojunction (c) and p-n junction (d)^[92]

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图 11 光催化CO₂还原机制示意图^[124]

Figure 11. Schematic diagram of photocatalytic CO₂ reduction mechanism^[124]

SHE—Standard hydrogen electrode

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图 12 Li-BiOF复合材料的制备及其金属锂剥离/电镀行为示意图^[131]

Figure 12. Schematic illustration of the fabrication and the metallic Li stripping/plating behavior of the Li-BiOF composite^[131]

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图 13 n-Al/BiOF燃烧反应机制示意图^[135]

Figure 13. Schematic diagram of the combustion reaction mechanism of n-Al/BiOF^[135]

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表 1 BiOF的制备方法

Table 1. Preparation method of BiOF

Preparation method	Bismuth source	Fluoride source	Reaction condition	Advantage and disadvantage	Ref.
Solvothermal method	Bi(NO₃)₃·5H₂O	NH₄F/NaF/HF	pH=6-10 120-200℃	Advantage: Economical and environmentally friendly, easy to operate, with small product particle size, high purity, and easy to control morphology; Disadvantage: High temperature and high pressure conditions are required, resulting in high equipment investment and difficulty in mass production	[31, 36-45]
Coprecipitation method	Bi(NO₃)₃·5H₂O	NH₄F	Room temperature, 8 h; 400℃, 2 h	Advantage: Simple, easy to operate, low cost, mild reaction conditions, suitable for industrial production; Disadvantage: Easy aggregation, poor crystallinity, and uneven particle size distribution	[18, 46-55]
Solid-state sintering method	Bi₂O₃	HF	425℃, 12 h	Advantage: Beneficial for preparing materials with high density, strength, and uniform structure; Disadvantage: Strict temperature conditions and difficulty in controlling particle size	[56-59]
Ion exchange method	BiOCl	NH₄F	170℃, 6 h	Advantage: Achieve precise control and optimization of materials, with high efficiency, and can be used in large-scale production; Disadvantage: Difficulty in regenerating exchange agents, high waste treatment and cost	[60-64]
Mechanochemical method	Bi₂O₃	BiF₃	700 r/min, 2 h	Advantage: Environmentally friendly, with short reaction time; Disadvantage: High energy consumption, possible introduction of impurities during the preparation process, and easy wear of equipment	[38, 65-72]

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表 2 BiOF离子掺杂改性的制备方法及改性效果

Table 2. Preparation method and modification effect of BiOF ion doping modification

Photocatalyst		Preparation method	Modification effect	Ref.
Metal ion doping	Ag-BiOF	Solvothermal method	The degradation rate of methylene blue (MB) under visible light is significantly better than that of pure BiOF.	[87]
	Ti-BiOF	Coprecipitation method	The electrochemical performance test results show that 5% Ti-BiOF material has higher specific capacity and better rate performance than pure BiOF.	[88]
	Pd-BiOF	Solvothermal method	Pd-BiOF exhibits strong absorption in both infrared and visible spectra, significantly enhancing its photocatalytic performance.	[89]
	Eu³⁺-BiOF	Solid-state sintering method	Rhodamine B (RhB) is completely degraded under visible light for 75 min.	[90]
	Er³⁺-BiOF	Coprecipitation method	The luminescence characteristics of BiOF submicron particles activated by Er³⁺ have potential applications in ratio thermometers.	[91]
	Sm³⁺-BiOF	Solid-state sintering method	The photocatalytic activity of 0.11Sm³⁺-BiOF is the best, and RhB is completely degraded at 180 min.	[15]
	Er³⁺/Yb³⁺-BiOF	Solid-state sintering method	Er³⁺/Yb³⁺ co-doped BiOF almost completely degrades RhB after 40 min.	[32]
	Tm³⁺/Yb³⁺-BiOF	Solvothermal method	Tm³⁺/Yb³⁺-BiOF enhances the degradation effect of RhB.	[30]
Non-metallic element doping	F-BiOF	Solvothermal method	F self doped layered BiOF enhances the internal electric field of the crystal and increases the luminescence intensity.	[31]

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表 3 BiOF异质结及其光催化活性总结

Table 3. Summary of BiOF heterojunction and its photocatalytic activity

Photocatalyst	Preparation method	Heterojunction type	Modification effect	Ref.
BiOF/BiFeO₃	Hydrothermal method	Type-I heterojunction	The photocatalytic coupling of benzylamine to N-benzylidene benzylamine using BiOF/BiFeO₃ can achieve a high conversion rate of 80%, which is 2.1 times higher than pure BiOF.	[98]
BiOBr/BiOF	Hydrothermal method	Type-II heterojunction	The maximum degradation rates of RhB and nitrobenzene by BiOBr/BiOF under visible light irradiation are 100% (25 min) and 94% (300 min), respectively.	[99]
BiOF/BiOCl_0.75Br_0.25	Ultrasonic assisted alcoholysis method	Type-II heterojunction	Under visible light, the degradation rate of RhB by BiOF/BiOCl_0.75Br_0.25 reaches 97% after 45 min.	[100]
BiOF/Bi₂O₃	Solvothermal method	Type-II heterojunction	In the presence of H₂O₂, the degradation rate of RhB by BiOF/Bi₂O₃ is close to 100% after 30 min of visible light irradiation.	[101]
BiOF/TiO₂	Solid-state sintering method	Type-II heterojunction	Under visible light, the degradation rate of RhB by BiOF/TiO₂ reaches 91.2%, which is 7 times higher than that of pure BiOF.	[59]
Ag₂O/BiOF	Coprecipitation method	Z-scheme heterojunction	Under simulated sunlight and visible light irradiation, Ag₂O/BiOF exhibits higher photocatalytic activity for the degradation of RhB compared to pure BiOF.	[102]
CdS/BiOF g-C₃N₄/BiOF	—	Z-scheme heterojunction	Both CdS/BiOF and g-C₃N₄/BiOF can efficiently photolysis and catalytic oxidation of formaldehyde at room temperature.	[103]
BiOCl/BiOF	Mechanochemical method	p-n junction	The degradation activity of BiOCl/BiOF on methyl orange (MO) is better than that of pure BiOF, and the degradation rate reaches 95% at 70 min.	[104]
BiOF/BiOI	Solvothermal method	p-n junction	Under visible light, the degradation rate of crystal violet (CV) and hydroxybenzoic acid (HBA) by BiOF/BiOI reaches 85%, with a rate constant 100 times higher than that of pure BiOF.	[105]
BiOF@ZIF-8	One-pot synthesis method	p-n junction	BiOF@ZIF-8 is used for selective green oxidation of alcohols, as an efficient multiphase catalyst.	[41]
BiVO₄/BiOF	Hydrothermal method	p-n junction	Under visible light, BiVO₄/BiOF can completely degrade MB.	[106]
In-MOF/BiOF	Hydrothermal method	p-n junction	20%In-MOF/BiOF exhibits effective and complete degradation of perfluorooctanoic acid (PFOA) (15 mg/L) under illumination.	[107]

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