Preparation and current applications of black titanium dioxide nanomaterials

doi:10.16085/j.issn.1000-6613.2023-2275

Abstract

Abstract:

Titanium dioxide (TiO₂) is a kind of typical semiconductor material and widely used in photocatalysis, however, its wide energy band gap limits its practical application. Black TiO₂ (B-TiO₂) nanomaterials can effectively improve their visible light-response performance and quantum efficiency through constructing structural defects on TiO₂ surface to reduce the band gap, which has attracted great attention. This paper introduced the basic properties of B-TiO₂ such as optical property, crystal types, defects and microstructures, and systematically summarized the methods of preparation and defect construction of black TiO₂ in recent years, including calcination, sol-gel and chemical reduction etc. It was also summarized the improvement strategy of performance for black TiO₂ and its application in water purification, medical treatment, energy conversion and other fields. Finally, the future research of B-TiO₂ needed to focus on the following aspects. The building of structure-activity relationship in depth from theory and experiment was basic for reasonable design of surface defects and development of efficient synthesis methods for B-TiO₂, which called for more advanced characterization and analysis tools. Besides, it was an important prerequisite to further enhance the structural stability of B-TiO₂ with high activity for practical application. The development of interdisciplinary disciplines should promote the applications of B-TiO₂ to various fields.

Key words: black titanium dioxide, photocatalysis, degradation, composites, nanomaterials

摘要：

二氧化钛（TiO₂）是典型的氧化物半导体材料，广泛应用于光催化领域，但其较宽的能量带隙限制了其在实际中的应用。黑色TiO₂（B-TiO₂）纳米材料通过在TiO₂表面构筑结构缺陷降低带隙宽度，能够有效提高其可见光响应性能和量子效率。本文总结了B-TiO₂的基本特性，包括光学性质、晶型、缺陷与微观结构性质，并对近年来B-TiO₂的制备与缺陷构筑方法（如气氛焙烧法、溶胶-凝胶法、化学还原法等）进行了系统总结。同时，本文梳理了黑色TiO₂性能提升策略及其在水体净化、有机物降解、能源转换及医疗等领域的应用现状。最后指出B-TiO₂研究领域未来需要重点关注的几个方面为：结合理论和实验深入探讨其结构-性能之间的构效关系是合理设计B-TiO₂表面缺陷、开发高效合成方法的基础，先进的表征和分析手段有待加强；在保持高活性的同时，开发结构更加稳定的B-TiO₂是将其推向实际应用的重要前提；此外，交叉学科的发展应推动B-TiO₂的应用范围向更多领域延伸。

关键词: 黑色二氧化钛, 光催化, 降解, 复合材料, 纳米材料

CLC Number:

TB332

LIU Wei, ZHANG Min, ZHU Zhaoqi, WANG Yi, LIANG Weidong, SUN Hanxue. Preparation and current applications of black titanium dioxide nanomaterials[J]. Chemical Industry and Engineering Progress, 2025, 44(1): 341-353.

刘炜, 张敏, 朱照琪, 王毅, 梁卫东, 孙寒雪. 黑色二氧化钛纳米材料的构筑及其应用现状[J]. 化工进展, 2025, 44(1): 341-353.

Figures/Tables 6

References 60

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样品名称	合成方法	带隙宽度 /eV	吸光波长 /nm	微观结构	缺陷类型	参考文献
黑色 TiO₂ 纳米晶体	气氛焙烧法（H₂）	1.26	—	无序工程纳米晶体结构	Ti³⁺，氧空位	[5]
黑色 TiO₂ 纳米粒子	气氛焙烧法（真空）	2.07	200~1000	介孔颗粒结构	Ti³⁺，氧空位	[20-21]
掺杂氮的黑色TiO₂	气氛焙烧法（N₂）	1.47	400~500	锐钛矿相晶体结构	N元素，氧空位，Ti³⁺	[14]
黑色TiO₂	铝热还原法	3.02	—	超薄空心球	表面积，氧空位	[9]
黑色TiO₂	铝热还原法盐酸酸洗法	2.4~2.8	600~800	纯锐钛矿晶体结构	结构无序、氧空位	[22]
高度畸变S/C/Ti³⁺掺杂的黑色TiO₂	溶胶-凝胶法	2.53	—	球形纳米结构	Ti³⁺，氧空位	[15]
具有核壳结构的黑色TiO₂	溶胶-凝胶法	2.96	400~600	核壳结构	Ti³⁺	[23]
具有可控晶格无序的黑色TiO₂	溶剂挥发诱导自组装法化学还原法	2.65	400~800	空心球结构	Ti³⁺，比较大的比表面积，较高的无序度	[24]
具有反蛋白石结构的负载镍的黑色TiO₂	模板法气氛焙烧法（H₂）	1.71	400~800	IO结构	Ti³⁺，掺杂元素Ni	[13]
黑色TiO₂纳米胶体	脉冲激光辐照法	1.9	400~500	球形核结构	氧空位，晶格缺陷	[25]
掺杂碳黑的锐钛矿型TiO₂纳米棒	气氛焙烧法（N₂）	2.4~3.2	350~450	短纳米棒结构	Ti³⁺，氧空位，杂质掺杂	[26]
黑色TiO₂纳米板	气氛焙烧法（Ar₂）	1.5	500~600	非晶态结构	氧空位，无序结构，Ti³⁺	[27]

样品名称	合成方法	带隙宽度 /eV	吸光波长 /nm	微观结构	缺陷类型	参考文献
黑色 TiO₂ 纳米晶体	气氛焙烧法（H₂）	1.26	—	无序工程纳米晶体结构	Ti³⁺，氧空位	[5]
黑色 TiO₂ 纳米粒子	气氛焙烧法（真空）	2.07	200~1000	介孔颗粒结构	Ti³⁺，氧空位	[20-21]
掺杂氮的黑色TiO₂	气氛焙烧法（N₂）	1.47	400~500	锐钛矿相晶体结构	N元素，氧空位，Ti³⁺	[14]
黑色TiO₂	铝热还原法	3.02	—	超薄空心球	表面积，氧空位	[9]
黑色TiO₂	铝热还原法盐酸酸洗法	2.4~2.8	600~800	纯锐钛矿晶体结构	结构无序、氧空位	[22]
高度畸变S/C/Ti³⁺掺杂的黑色TiO₂	溶胶-凝胶法	2.53	—	球形纳米结构	Ti³⁺，氧空位	[15]
具有核壳结构的黑色TiO₂	溶胶-凝胶法	2.96	400~600	核壳结构	Ti³⁺	[23]
具有可控晶格无序的黑色TiO₂	溶剂挥发诱导自组装法化学还原法	2.65	400~800	空心球结构	Ti³⁺，比较大的比表面积，较高的无序度	[24]
具有反蛋白石结构的负载镍的黑色TiO₂	模板法气氛焙烧法（H₂）	1.71	400~800	IO结构	Ti³⁺，掺杂元素Ni	[13]
黑色TiO₂纳米胶体	脉冲激光辐照法	1.9	400~500	球形核结构	氧空位，晶格缺陷	[25]
掺杂碳黑的锐钛矿型TiO₂纳米棒	气氛焙烧法（N₂）	2.4~3.2	350~450	短纳米棒结构	Ti³⁺，氧空位，杂质掺杂	[26]
黑色TiO₂纳米板	气氛焙烧法（Ar₂）	1.5	500~600	非晶态结构	氧空位，无序结构，Ti³⁺	[27]

B-TiO₂	合成方法	目标分子	降解率	降解机理	参考文献
金红石型黑色TiO₂	化学还原法、气氛焙烧法（Ar）	亚甲基蓝	100%（10^-5mol/L，20min）	较窄的带隙显示出较宽的吸光度，且降低了光电子的重组速率，增强了载流子的迁移，产生的H⁺和·OH是降解亚甲基蓝分子的主要活性物种	[35]
三元碳球(CSs)/ TiO_2-_x @碳化氮(CN)	化学还原法	2,4,6-三氯苯酚	>90%（10mg/L，150min）	TiO_2-_x /g-C₃N₄异质结与CSs结构中Ti-O-C桥之间多层转移的有效电子传递，使其具有良好的可见光收集能力，同时高的比表面积为吸附和表面反应提供有效反应位点，反应生成·OH和电子空穴有效降解2,4,6-三氯苯酚	[36]
氢化的黑色TiO₂	气氛烘焙法（H₂）	蚁醛	57%（100mg/L，4h）	表面存在氧空位，并通过杂质缺陷电离产生大量电子；吸附在H-TiO₂/H-C-TiO₂表面的O₂与电子相互作用，转化为活性氧降解甲醛	[37]
黑色TiO₂纳米粒子	化学还原法、气氛焙烧法（N₂）	二甲苯	35.64%（60mg/L）	CuOTiO₂(mb)中Ti⁴⁺、Ti³⁺、Cu²⁺和Cu⁺的共存降低了e^--h⁺的复合速率，Cu-MOF前体引入的晶粒最小使其带隙变窄为2.75eV，显著提高了可见光下对二甲苯的去除效率	[38]
黑色TiO₂	气氛烘焙法（真空）	乙酰氨基酚	100% （1mg/L，3h）	黑色TiO₂样品的价带比OH^-/·OH的氧化还原电位更正，在光催化过程中具有较高的生成·OH自由基的电位	[12]
磁性γ-Fe₂O₃超薄纳米片修饰的介孔黑色TiO₂空心球	化学还原法、气氛烘焙法（H₂）	四环素	99.3%（10mg/L，50min）	辐照后的氧化活性物质主要有四种：羟基自由基、空穴、超氧阴离子和过氧化氢，这些活性氧化物在降解过程中攻击四环素的官能团使其分解	[39]
氮掺杂的黑色TiO₂	化学还原法、气氛烘焙法（Ar）	环丙沙星	100%（500mg/L，70min）	样品具有更高的光致电子空穴对分离效率，通过·OH自由基氧化分解环丙沙星	[40]
磁性Fe₂O₃修饰的介孔黑色TiO₂空心球	化学还原法、气氛烘焙法（H₂）	赛克津	99%（10mg /L，60min）	由于氧空位、Ti³⁺和Fe²⁺的形成，使TiO₂带隙明显缩小，有利于光生载流子的分离，在水介质中捕获溶解氧，从而形成超氧自由基和H₂O₂，孔洞与水或OH^-反应，使赛克津分子完全矿化	[41]

B-TiO₂	合成方法	目标分子	降解率	降解机理	参考文献
金红石型黑色TiO₂	化学还原法、气氛焙烧法（Ar）	亚甲基蓝	100%（10^-5mol/L，20min）	较窄的带隙显示出较宽的吸光度，且降低了光电子的重组速率，增强了载流子的迁移，产生的H⁺和·OH是降解亚甲基蓝分子的主要活性物种	[35]
三元碳球(CSs)/ TiO_2-_x @碳化氮(CN)	化学还原法	2,4,6-三氯苯酚	>90%（10mg/L，150min）	TiO_2-_x /g-C₃N₄异质结与CSs结构中Ti-O-C桥之间多层转移的有效电子传递，使其具有良好的可见光收集能力，同时高的比表面积为吸附和表面反应提供有效反应位点，反应生成·OH和电子空穴有效降解2,4,6-三氯苯酚	[36]
氢化的黑色TiO₂	气氛烘焙法（H₂）	蚁醛	57%（100mg/L，4h）	表面存在氧空位，并通过杂质缺陷电离产生大量电子；吸附在H-TiO₂/H-C-TiO₂表面的O₂与电子相互作用，转化为活性氧降解甲醛	[37]
黑色TiO₂纳米粒子	化学还原法、气氛焙烧法（N₂）	二甲苯	35.64%（60mg/L）	CuOTiO₂(mb)中Ti⁴⁺、Ti³⁺、Cu²⁺和Cu⁺的共存降低了e^--h⁺的复合速率，Cu-MOF前体引入的晶粒最小使其带隙变窄为2.75eV，显著提高了可见光下对二甲苯的去除效率	[38]
黑色TiO₂	气氛烘焙法（真空）	乙酰氨基酚	100% （1mg/L，3h）	黑色TiO₂样品的价带比OH^-/·OH的氧化还原电位更正，在光催化过程中具有较高的生成·OH自由基的电位	[12]
磁性γ-Fe₂O₃超薄纳米片修饰的介孔黑色TiO₂空心球	化学还原法、气氛烘焙法（H₂）	四环素	99.3%（10mg/L，50min）	辐照后的氧化活性物质主要有四种：羟基自由基、空穴、超氧阴离子和过氧化氢，这些活性氧化物在降解过程中攻击四环素的官能团使其分解	[39]
氮掺杂的黑色TiO₂	化学还原法、气氛烘焙法（Ar）	环丙沙星	100%（500mg/L，70min）	样品具有更高的光致电子空穴对分离效率，通过·OH自由基氧化分解环丙沙星	[40]
磁性Fe₂O₃修饰的介孔黑色TiO₂空心球	化学还原法、气氛烘焙法（H₂）	赛克津	99%（10mg /L，60min）	由于氧空位、Ti³⁺和Fe²⁺的形成，使TiO₂带隙明显缩小，有利于光生载流子的分离，在水介质中捕获溶解氧，从而形成超氧自由基和H₂O₂，孔洞与水或OH^-反应，使赛克津分子完全矿化	[41]

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