铋基光催化剂的金属或非金属改性研究进展

doi:10.3866/PKU.WHXB202305048

摘要/Abstract

摘要：

随着经济的快速增长，环境和能源问题日益突出。太阳能作为一种可再生、环保的能源，受到了许多研究人员的关注，最大限度地利用太阳能资源成为未来的研究热点。众所周知，光催化技术可以将太阳能转化为化学能或电能，为环境污染提供解决方案。因此，半导体光催化技术被认为是解决能源危机和环境问题的最环保的技术之一。铋基半导体材料由于合适的能带结构、丰富的种类、无毒性和低成本，在光催化领域受到欢迎。然而，纯Bi基光催化剂存在光激发电子-空穴对复合效率高、量子产率低和光吸收能力有限的问题，导致光催化性能低。为了克服这些限制，人们设计了各种策略，比如金属或非金属掺杂、金属沉积、异质结构建和诱导缺陷生成来提高它们的光催化活性。在这些策略中，元素掺杂或金属沉积被认为是调整铋基材料能带结构和物化性质的有效方法。这个方法拓宽了光响应范围和提高了光催化性能。这篇综述总结了金属掺杂、非金属掺杂、金属和非金属共掺杂以及金属沉积改性铋基材料的最新研究进展。它也探索了它们在光催化降解污染物和重金属离子、氮气还原、二氧化碳还原、光催化抗菌等各个领域的应用。关于金属掺杂，我们将其分为三类：碱金属或碱土金属掺杂、过渡金属掺杂和稀土金属掺杂，并详细介绍了每种掺杂的优缺点。非金属掺杂则被分为卤素掺杂和非卤素掺杂，并重点研究非金属掺杂对铋基材料的影响。此外，我们还纵向比较了每个元素的优点。结合最近的研究进展，简要介绍了结合金属和非金属元素优点的共掺杂。对于金属沉积，我们主要从肖特基势垒和局域表面等离子体共振(LSPR)效应两个方面介绍了对Bi基材料的影响。最后，我们也呈现了金属或非金属改性Bi基光催化剂目前面临的挑战和前景。

关键词: 铋基光催化剂, 金属掺杂, 非金属掺杂, 共掺, 金属沉积, 电子结构

Abstract:

With the rapid growth of the economy, environmental and energy issues have become increasingly prominent. Solar energy, as a renewable and environmentally friendly energy source, has attracted the attention of many researchers. Maximizing the utilization of solar energy resources has become a hot research topic in the future. It is well known that photocatalytic technology can convert solar energy into chemical or electric energy, offering a solution to environmental pollution. Therefore, semiconductor photocatalytic technology has been recognized as one of the most eco-friendly approaches for addressing energy crises and environmental pollution. Bismuth-based semiconductor materials, have gained popularity in the field of photocatalysis due to their suitable band structure, wide range of variations, non-toxicity, and low cost. However, pure Bi-based photocatalysts suffer from high recombination efficiency of photoexcited electron-hole pairs, poor quantum yield and limited light absorption ability, resulting in low photocatalytic performance. To overcome these limitations, various strategies such as metal or nonmetal doping, metal deposition, construction of heterojunctions and inducing defect generation have been employed to enhance their photocatalytic performance. Among these strategies, element doping or metal deposition is considered an effective approach for adjusting the band structure and physicochemical properties of bismuth-based materials. This extends the range of light response and improves photocatalytic performance. This mini review aims to summarize the recent research progress in Bi-based materials modified by metal doping, nonmetal doping, metal and nonmetal co-doping, and metal deposition. It also explores their applications in different fields, including photocatalytic removal of pollutants and heavy metal ions, nitrogen reduction, carbon dioxide reduction, and photocatalytic antibacterial, etc. Regarding metal doping, we classify it into three categories: alkali or alkaline earth metals doping, transition metal doping, and rare earth metal doping, and provide a detailed introduction to the advantages and disadvantages of each type of doping. Nonmetallic doping is categorized into halogen and non-halogen doping, with a focus on the impact of nonmetallic doping on bismuth-based materials. Furthermore, we present a vertical comparison of the advantages of each element vertically. Co-doping, which combines the advantages of both metal and nonmetal elements, is briefly outlined in terms of recent research progress. In the case of metal deposition, we mainly discuss the impact on Bi based materials from two aspects: the Schottky barrier and the localized surface plasmon resonance (LSPR) effect. Finally, we also discuss the current challenges and prospects faced by metal or nonmetal modified Bi-based photocatalysts.

Key words: Bismuth based photocatalyst, Metal doping, Nonmetal doping, Co-doping, Metal deposition, Electronic structure

丁慧伟, 彭博, 王志豪, 韩巧凤. 铋基光催化剂的金属或非金属改性研究进展[J]. 物理化学学报, 2024, 40(4), 2305048. doi: 10.3866/PKU.WHXB202305048

Huiwei Ding, Bo Peng, Zhihao Wang, Qiaofeng Han. Advances in Metal or Nonmetal Modification of Bismuth-Based Photocatalysts[J]. Acta Phys. -Chim. Sin. 2024, 40(4), 2305048. doi: 10.3866/PKU.WHXB202305048

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202305048

https://www.whxb.pku.edu.cn/CN/Y2024/V40/I4/2305048

图/表 15

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表1

Types of metal doping	Dopants	Ionic radius Bi (1.03 Å)	Pristine materials	Light source	Application	Enhanced photocatalytic Activity/pristine	Ref.
Alkali metals	Na	1.02 Å	α-Bi₂O₃	λ > 420 nm	RhB degradation	0.0245 min⁻¹/0.0081 min⁻¹	35
	Cs	1.74 Å	α-Bi₂O₃	λ > 420 nm	MB degradation	0.0765 min⁻¹/0.0125 min⁻¹	31
	Sr	1.12 Å	BiOI	λ > 420 nm	Indomethacin degradation	0.0574 min⁻¹/0.0053 min⁻¹	36
	Ba	1.35 Å	BiOBr	λ ≥ 420 nm	NO oxidation	53%/10% (5 min)	39
	Ba	1.35 Å	BiFeO₃	Natural sunlight	RhB degradation	86%/57% (6 h)	41
Transition metals	Ti	0.6 Å	β-Bi₂O₃	λ > 420 nm	Pentachlorophenol reduction	99.6% within 60 min	49
	Ti	0.6 Å	BiOI	λ ≥ 400 nm	Diclofenac sodium salt degradation	0.0483 min⁻¹/0.004 min⁻¹	50
	Mn	0.83 Å	BiOCl	Visible light	Nile blue degradation	0.36 min⁻¹/0.02 min⁻¹	42
	Fe	0.64 Å	Bi₂MoO₆	λ > 420 nm	RhB degradation	92.4%/66.3% (90 min)	64
	Fe		δ-Bi₂O₃	UV light	Paracetamol degradation	−	65
	Fe		BiOCl	λ ≥ 400 nm	Cr reduction RhB degradation	0.061 min⁻¹/0.012 min⁻¹ 0.077 min⁻¹/0.019 min⁻¹	63
	Co	0.65 Å	BiOBr	λ > 400 nm	RhB degradation MB degradation	99.5%/34% (120 min) 98.9%/50.6% (150 min)	51
	Co		BiOBr_xCl_1−x	Visible light	RhB degradation E. coli bacteria inactivation	0.024 min⁻¹/0.0096 min⁻¹; –	52
	Co		BiOCl	λ > 420 nm	RhB degradation Norfloxacin (NOR) degradation Cr reduction	98.9%/69.3% (5 min) 82.3%/48.1% (7 min) 81.5%/62.7% (7 min)	54
	Co		BiOCl	λ > 420 nm	Bisphenol A (BPA) degradation	95%/20% (120 min)	53
	Cu	0.73 Å	BiOCl	400 nm ≤ λ ≤ 800 nm	RhB degradation	99.1%/68.6% (120 min)	22
	Cu		Bi₂Se₃	Sunlight	MB degradation malachite green (MG) degradation	0.123 min⁻¹/0.043 min⁻¹ 0.151 min⁻¹/0.041 min⁻¹	61
	Cu		BiOBr	λ > 420 nm	NOR degradation	0.64 min⁻¹/0.28 min⁻¹	58
	Zn	0.74 Å	BiOCl	λ > 420 nm	RhB degradation	0.46019 min⁻¹/0.17055 min⁻¹	55
	Mo	0.62 Å	BiVO₄	Sunlight	Water splitting	–	43
	Ag	1 Å	Bi₂WO₆	Visible light	RhB degradation	94%/50% (120 min)	70
	Ag		BiOI	Daylight	MB degradation	96.8%/81.89% (100 min)	67
	Au	0.84 Å	Bi₂MoO₆	Visible light	RhB degradation	0.0107 min⁻¹/0.00193 min⁻¹	69
	Pd	0.64 Å	Bi₂MoO₆	Visible light	RhB degradation	97.12%/38.36% (240 min)	68
Rare earth metals	La	1.03 Å	Bi₂O₃CO₃	λ > 420 nm	NO oxidation	49.8%/15.2% (30 min)	104
	La		BiOCl	Visible light	RhB degradation Cr reduction	94.7%/45.2% (18 min) 94.3%/7.1% (120 min)	100
	La Sm	1.03 Å 0.96 Å	Bi₅O₇I	λ ≥ 420 nm	Tetracycline (TC) degradation RhB degradation	100%/50% (40 min) 93%/0 (40 min)	99
	Ce	1.20 Å	BiPO₄	UV light	MB degradation	90%/− (120 min)	91
	Ce		BiOBr	380 nm ≤ λ ≤ 780 nm	RhB degradation	99.22%/71.04% (40 min)	92
	Pr	0.99 Å	α-Bi₂O₃	λ > 420 nm	RhB degradation 2, 4-dichlorophenol degradation	70.8%/48.7% (120 min) 81.8%/42.8% (120 min)	94
	Sm	0.96 Å	BiFeO₃	λ ≥ 420 nm	Methyl orange (MO) degradation	86.9%/58.8% (120 min)	93
	Eu	0.95 Å	BiVO₄	Visible light	MB degradation RhB degradation	90.1%/60.8% (90 min) 60.1%/40.5% (90 min)	85
	Eu		Bi₂O₃	λ > 420 nm	RhB degradation	−	90
	Gd	0.94 Å	Bi₂Fe₄O₉	Visible light	MB degradation	77%/50% (80 min)	89
	Gd		β-Bi₂O₃	λ > 400 nm	MO degradation RhB degradation Phenol degradation	993.%/70.1% (28 min) 98.2%/29.8% (120 min) 97.2%/72.3% (195 min)	88
Rare earth metals	Er	0.89 Å	BiOBr	Visible light	RhB degradation	92.7%/59.3% (100 min)	79
	Er	0.89 Å	BiOI_0.5Cl_0.5	λ > 420 nm	Acid Red1 degradation	0.0909 min⁻¹/0.0513 min⁻¹	87
	Er Yb	0.89 Å 0.98 Å	Bi₂MoO₆	Solar light	RhB degradation	–	95
	Gd Er Lu	0.94 Å 0.89 Å 0.86 Å	Bi₂MoO₆	λ > 420 nm	TC degradation RhB degradation 4-Chlorophenol degradation	−	98
Self-doping	Bi vacancies		Bi₂WO₆	λ > 420 nm	Water splitting	100.13 μmol∙g ⁻¹∙h⁻¹/ 38.01 μmol∙g ⁻¹∙h⁻¹	107
Self-doping	Bi vacancies		BiOBr	Solar light	CO₂ reduction	20.1 μmol∙g ⁻¹∙h⁻¹/5.3 μmol∙g ⁻¹∙h⁻¹	108

表1

图8

图9

表2

Types of nonmetal doping	Dopants	Ionic radius	Pristine materials	Light source	Application	Enhanced photocatalytic Activity/pristine	Ref.
Halogen	Cl	1.8 Å (Cl)/ 1.4 Å (O)	BiOI	λ > 420 nm	MB degradation	0.01203 min⁻¹/0.00148 min⁻¹	119
	Cl	1.8 Å (Cl)/ 1.4 Å (O)	Bi₂O₂CO₃	Sunlight	RhB degradation	0.1679 min⁻¹/0.0708 min⁻¹	120
	Br	1.9 Å	BiOCOOH	λ > 420 nm	NO oxidation	37.8%/almost no activity	112
	Br	1.9 Å	Bi₂MoO₆	λ ≥ 420 nm	N₂ reduction	1.60 μmol∙h⁻¹/0.68 μmol∙h⁻¹	23
	I	2.20 Å	Bi₁₂O₁₇Cl₂	λ > 420 nm	MO degradation	96.1%/33.7% (60 min)	113
	I		BiOIO₃	λ > 420 nm	Bisphenol AF degradation Bisphenol A (BPA) degradation	0.02787 min⁻¹/0.00002 min⁻¹ 0.06764 min⁻¹/0.00004 min⁻¹	117
	I		Bi₂O₂CO₃	λ > 400 nm	MO degradation	About 20%/13.0% (35 min)	114
	I		BiOIO₃	λ > 420 nm	Propylparaben degradation	97.2%/barely change (60 min)	122
	I		Bi₂GdO₄Cl	λ ≥ 420 nm	Water splitting	14.8 μmol∙h⁻¹/3.4 μmol∙h⁻¹	116
	Cl, Br, I		Bi₂O₂(OH)(NO₃)	Solar irradiation	CO₂ reduction	8.12 µmol∙g⁻¹∙h⁻¹ (Br)/ 0.11 µmol∙g⁻¹∙h⁻¹	111
	I		Bi₄Ti₃O₁₂	Solar irradiation	CO₂ reduction	10.8 µmol∙g⁻¹∙h⁻¹ (Br)/ 1.7 µmol∙g⁻¹∙h⁻¹	118
	Cl, Br, I		Bi₂MoO₆	Solar irradiation	N₂ reduction	10.56 µmol∙g⁻¹∙h⁻¹ (I)/ 3.00 µmol∙g⁻¹∙h⁻¹	121
Non halogen	B	0.27 Å	Bi₃O₄Cl	420 nm ≤ λ ≤ 800 nm	Ciprofloxacin degradation	91.2 %/barely change (12 h)	128
	C	0.16 Å	BiOCl	λ > 420 nm	NO oxidation	40.6%/5.4% (5 min)	133
	C		Bi₃O₄Cl	λ ≥ 420 nm	Water splitting	80%/0.6%	134
	C		Bi₂MoO₆	Visible light	NO oxidation	60.0%/29.9% (230 min)	135
	C		BiOI	Sunlight Visible light	N₂ reduction MO degraddation	311 µmol∙L⁻¹∙g⁻¹∙h⁻¹/83.6 µmol∙L⁻¹∙g⁻¹∙h⁻¹ 0.136 min⁻¹/0.025 min⁻¹	132
	N	1.71 Å (N³⁻)	Bi₂WO₆	λ > 290 nm	RhB degradation	90%/30%–45% (60 min)	129
	Si	0.42 Å	Bi₂O₂CO₃	Visible light	RhB degradation MO degradation MB degradation	50%/− 10%/− 80%/−	130
	P	0.34 Å	BiO_x	Visible light	Cr degradation RhB degradation	84%/67% (180 min) 96%/81% (120 min)	125
	P	0.34 Å	BiOCl	λ > 420 nm	TC degradation	81.0%/29.1% (30 min)	126

表2

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表3

图11

表4

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