黑色二氧化钛纳米材料的构筑及其应用现状

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

摘要/Abstract

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

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

中图分类号:

TB332

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.

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.

图/表 6

参考文献 60

1	RAJARAMAN T S, PARIKH Sachin P, GANDHI Vimal G. Black TiO₂: A review of its properties and conflicting trends[J]. Chemical Engineering Journal, 2020, 389: 123918.
2	LIAO Lijun, WANG Mingtao, LI Zhenzi, et al. Recent advances in black TiO₂ nanomaterials for solar energy conversion[J]. Nanomaterials, 2023, 13(3): 468.
3	DETTE Christian, PÉREZ-OSORIO Miguel A, KLEY Christopher S, et al. TiO₂ anatase with a bandgap in the visible region[J]. Nano Letters, 2014, 14(11): 6533-6538.
4	张甄, 王宝冬, 徐文强, 等. 黑色二氧化钛纳米材料研究进展[J]. 材料导报, 2019, 33(S1): 8-15.
	ZHANG Zhen, WANG Baodong, XU Wenqiang, et al. Research progress of black titanium dioxide nanomaterials[J]. Materials Reports, 2019, 33(S1): 8-15.
5	CHEN Xiaobo, LIU Lei, YU Peter Y, et al. Increasing solar absorption for photocatalysis with black hydrogenated titanium dioxide nanocrystals[J]. Science, 2011, 331(6018): 746-750.
6	WANG Xiangdong, FU Rong, YIN Qianqian, et al. Black TiO₂ synthesized via magnesiothermic reduction for enhanced photocatalytic activity[J]. Journal of Nanoparticle Research, 2018, 20(4): 89.
7	YU Xiaomei, KIM Boseong, KIM Yu Kwon. Highly enhanced photoactivity of anatase TiO₂ nanocrystals by controlled hydrogenation-induced surface defects[J]. ACS Catalysis, 2013, 3(11): 2479-2486.
8	SINHAMAHAPATRA Apurba, JEON Jong-Pil, YU Jong-Sung. A new approach to prepare highly active and stable black titania for visible light-assisted hydrogen production[J]. Energy & Environmental Science, 2015, 8(12): 3539-3544.
9	SONG Hui, LI Chenxi, LOU Zirui, et al. Effective formation of oxygen vacancies in black TiO₂ nanostructures with efficient solar-driven water splitting[J]. ACS Sustainable Chemistry & Engineering, 2017, 5(10): 8982-8987.
10	LI Zhe, WANG Engui, ZHANG Yingzi, et al. Antibacterial ability of black titania in dark: Via oxygen vacancies mediated electron transfer[J]. Nano Today, 2023, 50: 101826.
11	张开富. 多孔黑二氧化钛及其复合体的制备与光催化性能研究[D]. 哈尔滨: 黑龙江大学, 2016.
	ZHANG Kaifu. Preparation and photocatalytic properties of porous black titanium dioxide and its complex[D]. Harbin: Helongjiang University, 2016.
12	KATAL Reza, SALEHI Mojtaba, FARAHANI Mohammad Hossein Davood Abadi, et al. Preparation of a new type of black TiO₂ under a vacuum atmosphere for sunlight photocatalysis[J]. ACS Applied Materials & Interfaces, 2018, 10(41): 35316-35326.
13	YE Jin, HE Jiahui, WANG Shuang, et al. Nickel-loaded black TiO₂ with inverse opal structure for photocatalytic reduction of CO₂ under visible light[J]. Separation and Purification Technology, 2019, 220: 8-15.
14	ZHOU Li, CAI Min, ZHANG Xu, et al. In-situ nitrogen-doped black TiO₂ with enhanced visible-light-driven photocatalytic inactivation of Microcystis aeruginosa cells: Synthesization, performance and mechanism[J]. Applied Catalysis B: Environmental, 2020, 272: 119019.
15	PATIL Shivaraj B, PHATTEPUR Harish, NAGARAJU G, et al. Highly distorted mesoporous S/C/Ti³⁺ doped black TiO₂ for simultaneous visible light degradation of multiple dyes[J]. New Journal of Chemistry, 2020, 44(23): 9830-9836.
16	YANG Chongyin, WANG Zhou, LIN Tianquan, et al. Core-shell nanostructured “black” rutile titania as excellent catalyst for hydrogen production enhanced by sulfur doping[J]. Journal of the American Chemical Society, 2013, 135(47): 17831-17838.
17	WU Tong, FAN Jinchen, LI Qiaoxia, et al. Palladium nanoparticles anchored on anatase titanium dioxide-black phosphorus hybrids with heterointerfaces: Highly electroactive and durable catalysts for ethanol electrooxidation[J]. Advanced Energy Materials, 2018, 8(1): 1701799.
18	AN Ha-Rim, PARK So Young, Jin Young HUH, et al. Nanoporous hydrogenated TiO₂photocatalysts generated by underwater discharge plasma treatment for solar photocatalytic applications[J]. Applied Catalysis B: Environmental, 2017, 211: 126-136.
19	ZHENG Peiru, ZHANG Lishu, ZHANG Xingfan, et al. Hydrogenation of TiO₂ nanosheets and nanoparticles: Typical reduction stages and orientation-related anisotropic disorder[J]. Journal of Materials Chemistry A, 2021, 9(39): 22603-22614.
20	HAN Lijuan, AN Xingcai, ZHANG Ping, et al. The removal of formaldehyde via visible photocatalysis using the black TiO₂ nanoparticles with mesoporous[J]. ChemistrySelect, 2020, 5(1): 97-103.
21	ZHANG Xu, CAI Min, CUI Naxin, et al. Defective black TiO₂: Effects of annealing atmospheres and urea addition on the properties and photocatalytic activities[J]. Nanomaterials, 2021, 11(10): 2648.
22	LI Jun, WU Enhui, HOU Jing, et al. A facile method for the preparation of black TiO₂ by Al reduction of TiO₂ and their visible light photocatalytic activity[J]. RSC Advances, 2020, 10(57): 34775-34780.
23	HAIDER Sajjad, NAWAZ Rab, ANJUM Muzammil, et al. Property-performance relationship of core-shell structured black TiO₂ photocatalyst for environmental remediation[J]. Frontiers of Environmental Science & Engineering, 2023, 17(9): 111.
24	JIANG Xiongrui, YAN Zhiyao, ZHANG Jing, et al. Mesoporous hollow black TiO₂ with controlled lattice disorder degrees for highly efficient visible-light-driven photocatalysis[J]. RSC Advances, 2019, 9(63): 36907-36914.
25	RAVEENDRAN NAIR Pooja, ROSA SANTIAGO RAMIREZ Claudia, ANGEL GRACIA PINILLA Miguel, et al. Black titanium dioxide nanocolloids by laser irradiation in liquids for visible light photo-catalytic/electrochemical applications[J]. Applied Surface Science, 2023, 623: 157096.
26	LI Wenjuan, LIANG Robert, ZHOU Norman Y, et al. Carbon black-doped anatase TiO₂ nanorods for solar light-induced photocatalytic degradation of methylene blue[J]. ACS Omega, 2020, 5(17): 10042-10051.
27	KANG Jianxin, ZHANG Yan, CHAI Ziwei, et al. Amorphous domains in black titanium dioxide[J]. Advanced Materials, 2021, 33(23): e2100407.
28	GAMBOA Julio Andrade, PASQUEVICH Daniel M. Effect of chlorine atmosphere on the anatase-rutile transformation[J]. Journal of the American Ceramic Society, 1992, 75(11): 2934-2938.
29	Joohyun LIM, KIM Se-Ho, AYMERICH ARMENGOL Raquel Aymerich, et al. Atomic-scale mapping of impurities in partially reduced hollow TiO₂ nanowires[J]. Angewandte Chemie International Edition, 2020, 59(14): 5651-5655.
30	ZHU Guilian, YIN Hao, YANG Chongyin, et al. Black titania for superior photocatalytic hydrogen production and photoelectrochemical water splitting[J]. ChemCatChem, 2015, 7(17): 2614-2619.
31	XIAO Bo, YU Fang, XIA Yue, et al. Wood-based, bifunctional, mulberry-like nanostructured black titania evaporator for solar-driven clean water generation[J]. Energy Technology, 2022, 10(3): 2100679.
32	LI Zebiao, BIAN Haidong, XU Zhengtao, et al. Solution-based comproportionation reaction for facile synthesis of black TiO₂ nanotubes and nanoparticles[J]. ACS Applied Energy Materials, 2020, 3(7): 6087-6092.
33	ZHAN Xuepeng, XU Huailiang, LI Chunhao, et al. Remote and rapid micromachining of broadband low-reflectivity black silicon surfaces by femtosecond laser filaments[J]. Optics Letters, 2017, 42(3): 510-513.
34	SU Yue, ZHANG Wei, CHEN Shanming, et al. Engineering black titanium dioxide by femtosecond laser filament[J]. Applied Surface Science, 2020, 520: 146298.
35	GRABSTANOWICZ Lauren R, GAO Shanmin, LI Tao, et al. Facile oxidative conversion of TiH₂ to high-concentration Ti³⁺-self-doped rutile TiO₂ with visible-light photoactivity[J]. Inorganic Chemistry, 2013, 52(7): 3884-3890.
36	ZHU Chengzhang, CHEN Xiao, MA Jian, et al. Carbon nitride-modified defective TiO_2– _x @Carbon spheres for photocatalytic H₂ evolution and pollutants removal: Synergistic effect and mechanism insight[J]. The Journal of Physical Chemistry C, 2018, 122(35): 20444-20458.
37	ZENG Lei, SONG Wulin, LI Minghui, et al. Catalytic oxidation of formaldehyde on surface of H-TiO₂/H-C-TiO₂ without light illumination at room temperature[J]. Applied Catalysis B: Environmental, 2014, 147: 490-498.
38	ZHOU Wenjun, SHEN Boxiong, WANG Fumei, et al. Enhanced photocatalytic degradation of xylene by blackening TiO₂nanoparticles with high dispersion of CuO[J]. Journal of Hazardous Materials, 2020, 391: 121642.
39	REN Liping, ZHOU Wei, SUN Bojing, et al. Defects-engineering of magnetic γ-Fe₂O₃ ultrathin nanosheets/mesoporous black TiO₂ hollow sphere heterojunctions for efficient charge separation and the solar-driven photocatalytic mechanism of tetracycline degradation[J]. Applied Catalysis B: Environmental, 2019, 240: 319-328.
40	SARAFRAZ Mansour, SADEGHI Morteza, YAZDANBAKHSH Ahmadreza, et al. Enhanced photocatalytic degradation of ciprofloxacin by black Ti³⁺/N-TiO₂ under visible LED light irradiation: Kinetic, energy consumption, degradation pathway, and toxicity assessment[J]. Process Safety and Environmental Protection, 2020, 137: 261-272.
41	SUN Bojing, ZHOU Wei, LI Haoze, et al. Magnetic Fe₂O₃/mesoporous black TiO₂ hollow sphere heterojunctions with wide-spectrum response and magnetic separation[J]. Applied Catalysis B: Environmental, 2018, 221: 235-242.
42	CAREY John H, LAWRENCE John, TOSINE Helle M. Photodechlorination of PCB in the presence of titanium dioxide in aqueous suspensions[J].Bull of Environ Contam Toxic,1976,16(6): 697-701.
43	CAO Yan, XING Zipeng, SHEN Yingcai, et al. Mesoporous black Ti³⁺/N-TiO₂ spheres for efficient visible-light-driven photocatalytic performance[J]. Chemical Engineering Journal, 2017, 325: 199-207.
44	JIANG Jiaojiao, XING Zipeng, LI Meng, et al. In situ Ti³⁺/N-codoped three-dimensional (3D) urchinlike black TiO₂ architectures as efficient visible-light-driven photocatalysts[J]. Industrial & Engineering Chemistry Research, 2017, 56(28): 7948-7956.
45	XUE Chaorui, LI Dong, LI Yangsen, et al. 3D-carbon dots decorated black TiO₂ nanotube Array@Ti foam with enhanced photothermal and photocatalytic activities[J]. Ceramics International, 2019, 45(14): 17512-17520.
46	DU Jimin, WANG Huiming, CHEN Huijuan, et al. Synthesis and enhanced photocatalytic activity of black porous Zr-doped TiO₂ monoliths[J]. Nano, 2016, 11(6): 1650068.
47	ZHANG Hang, XING Zipeng, ZHANG Yan, et al. Ni²⁺ and Ti³⁺ Co-doped porous black anatase TiO₂ with unprecedented-high visible-light-driven photocatalytic degradation performance[J]. RSC Advances, 2015, 5(129): 107150-107157.
48	YANG Jingxia, ZHANG Jingjin, ZOU Bingjie, et al. Black SnO₂-TiO₂ nanocomposites with high dispersion for photocatalytic and photovoltalic applications[J]. ACS Applied Nano Materials, 2020, 3(5): 4265-4273.
49	CHEN Ping. A novel synthesis of Ti³⁺ self-doped Ag₂O/TiO₂ (p-n) nanoheterojunctions for enhanced visible photocatalytic activity[J]. Materials Letters, 2016, 163: 130-133.
50	LI Kai, HUANG Zhenyu, ZENG Xiaoqiao, et al. Synergetic effect of Ti³⁺ and oxygen doping on enhancing photoelectrochemical and photocatalytic properties of TiO₂/g-C₃N₄ heterojunctions[J]. ACS Applied Materials & Interfaces, 2017, 9(13): 11577-11586.
51	WANG Shanchi, CAI Jingsheng, MAO Jiajun, et al. Defective black Ti³⁺ self-doped TiO₂and reduced graphene oxide composite nanoparticles for boosting visible-light driven photocatalytic and photoelectrochemical activity[J]. Applied Surface Science, 2019, 467/468: 45-55.
52	WILKINSON John L, BOXALL Alistair B A, KOLPIN Dana W, et al. Pharmaceutical pollution of the world’s rivers[J]. Proceedings of the National Academy of Sciences of the United States of America, 2022, 119(8): e2113947119.
53	WU Suqing, LI Xueyan, TIAN Yanqin, et al. Excellent photocatalytic degradation of tetracycline over black anatase-TiO₂ under visible light[J]. Chemical Engineering Journal, 2021, 406: 126747.
54	ANDRONIC Luminita, GHICA Daniela, STEFAN Mariana, et al. Visible-light-active black TiO₂ nanoparticles with efficient photocatalytic performance for degradation of pharmaceuticals[J]. Nanomaterials, 2022, 12(15): 2563.
55	GAO Peiru, NOOR Nor Qhairul Izzreen Mohd, SHAARANI Sharifudin Md. Current status of food safety hazards and health risks connected with aquatic food products from Southeast Asian Region[J]. Critical Reviews in Food Science and Nutrition, 2022, 62(13): 3471-3489.
56	WANG Gongming, WANG Hanyu, LING Yichuan, et al. Hydrogen-treated TiO₂ nanowire arrays for photoelectrochemical water splitting[J]. Nano Letters, 2011, 11(7): 3026-3033.
57	ZHANG Changkun, YU Hongmei, LI Yongkun, et al. Supported noble metals on hydrogen-treated TiO₂ nanotube arrays as highly ordered electrodes for fuel cells[J]. ChemSusChem, 2013, 6(4): 659-666.
58	TOUNI Aikaterini, LIU Xin, KANG Xiaolan, et al. Methanol oxidation at platinum coated black titania nanotubes and titanium felt electrodes[J]. Molecules, 2022, 27(19): 6382.
59	LIU Ning, ZHU Ming, NIU Niu, et al. Aza-BODIPY probe-decorated mesoporous black TiO₂ nanoplatform for the highly efficient synergistic phototherapy[J]. ACS Applied Materials & Interfaces, 2020, 12(37): 41071-41078.
60	DAI Ting, HE Wenming, TU Shuangshuang, et al. Black TiO₂ nanoprobe-mediated mild phototherapy reduces intracellular lipid levels in atherosclerotic foam cells via cholesterol regulation pathways instead of apoptosis[J]. Bioactive Materials, 2022, 17: 18-28.

编辑推荐 0

Metrics

阅读次数

全文

HTML			PDF

最新录用	在线预览	正式出版	最新录用	在线预览	正式出版
0	0	3	0	0	27

来源	本网站	其他网站

次数	26	4
比例	87%	13%

摘要

最新录用	在线预览	正式出版

0	0	84

来源	本网站	其他网站

次数	17	67
比例	20%	80%

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]

[1]	李洪慧, 李青云, 李梅, 方艺燕, 沈慧婷, 林宏飞. 生物法处理典型难降解铁氰络合物[J]. 化工进展, 2025, 44(2): 1163-1169.
[2]	闫鹏程, 高卓凡, 周志辉, 吴红丹, 陈霞, 周显, 范泽宇, 邓闪闪, 鲁麒, 向媛. 聚酰胺/聚醚醚酮复合膜的制备及其有机溶剂纳滤性能[J]. 化工进展, 2025, 44(2): 1147-1156.
[3]	赵珂, 张恒, 翟倩, 甄琪, 苏天阳, 崔景强. PLA/PEG@SDS超细纤维水蒸发器的复合结构设计及其液体传输行为[J]. 化工进展, 2025, 44(2): 1014-1024.
[4]	游小银, 汪楚乔, 刘才华, 彭小明. Z型CN/NGBO/BV催化剂体系的构筑及光类芬顿降解四环素性能[J]. 化工进展, 2025, 44(1): 286-296.
[5]	吴迪, 彭明国, 谷宇, 毛林强, 张文艺. 磁性纳米破乳剂的制备及其稠油乳状液破乳性能[J]. 化工进展, 2025, 44(1): 436-444.
[6]	蒋莉萍, 张雪乔, 钟晓娟, 魏于凡, 肖利, 郭旭晶, 羊依金. 钒渣酸浸提铁工艺优化及复合光催化剂的制备[J]. 化工进展, 2025, 44(1): 538-548.
[7]	杜小聪, 辛春福, 赵钰. 路用复合相变材料及相变改性沥青性能评价[J]. 化工进展, 2024, 43(S1): 419-430.
[8]	马桂璇, 徐子桐, 肖志华, 宁国庆, 魏强, 徐春明. 氧硫双掺杂CNTs水系导电剂辅助构筑高性能石墨/SiO负极[J]. 化工进展, 2024, 43(S1): 443-456.
[9]	高觊兴, 丁玉梅, 张超, 谭晶, 丁熙, 李好义, 杨卫民. 熔体微分电纺PLA/PCL微纳米纤维膜的制备及其性能[J]. 化工进展, 2024, 43(S1): 457-468.
[10]	慕铭, 赵伟伟, 陈光孟, 刘小青. 基于激光诱导石墨烯的应变传感器研究进展[J]. 化工进展, 2024, 43(9): 4970-4979.
[11]	申纯宇, 李翠利, 汤建伟, 刘咏, 刘鹏飞, 丁俊祥, 申博, 王保明. 纳米氢氧化镁制备及其阻燃应用进展[J]. 化工进展, 2024, 43(9): 4980-4995.
[12]	李镇武, 蒲迪, 熊亚春, 吴定莹, 金诚, 郭拥军. 驱油用纳米材料在提高采收率方面研究进展[J]. 化工进展, 2024, 43(9): 5035-5048.
[13]	刘丽, 冯博, 文洋, 古启雄. 硅基介孔材料的合成、功能化及对金属的吸附研究进展[J]. 化工进展, 2024, 43(9): 5063-5078.
[14]	李美萱, 成建凤, 黄国勇, 徐盛明, 郁丰善, 翁雅青, 曹才放, 温嘉玮, 王俊莲, 王春霞, 顾斌涛, 张袁华, 刘斌, 王才平, 潘剑明, 徐泽良, 王翀, 王珂. 高电压镍锰酸锂正极材料的合成与电化学机理[J]. 化工进展, 2024, 43(9): 5086-5094.
[15]	楼高波, 姚潇翎, 倪静雯, 傅深渊, 刘丽娜. 离子络合物改性二维云母环氧树脂复合材料的制备及性能[J]. 化工进展, 2024, 43(9): 5142-5156.