Construction and application of heterostructures of photocatalyst TiO2 nanomaterials

doi:10.16085/j.issn.1000-6613.2025-0347

Abstract

Abstract:

TiO₂ photocatalysts exhibit strong oxidation capacity and chemical stability with structural design crucial for performance enhancement. Heterojunction construction serves as an effective strategy for optimizing TiO₂ photocatalytic performance. The charge transfer mechanisms in type-Ⅱ, p-n, Z-scheme, S-scheme and Schottky heterojunctions are analyzed with emphasis on TiO₂ nanomaterials exhibiting superior photocatalytic activity. Preparation methods and applications in organic pollutant degradation, harmful gas treatment, hydrogen production and biomedicine are summarized. Finally, an analysis of the construction of TiO₂ heterojunctions is conducted, proposing effective research directions to enhance the photocatalytic performance of TiO₂, and future prospects are discussed.

Key words: titanium dioxide, photocatalyst, heterojunction, nanomaterials, environment

摘要：

TiO₂光催化剂具有氧化能力强、化学稳定性高等优点，其结构的调控和设计对光催化反应性能的提高有着重要意义。科研人员发现构建异质结是提升TiO₂光催化性能的最有效的方法之一。本文总结了Ⅱ型、p-n型、Z型、S型、肖特基型5类异质结的机理，介绍了光催化性能优异的TiO₂纳米异质结材料，并对各类异质结的光催化性能进行了讨论分析。此外，本文还简述了制备异质结的方法以及TiO₂在有机废水的降解、有害气体的治理、光解水制氢和生物医药等方面的应用，展示了其重要价值。最后，针对TiO₂异质结的构建进行了分析，提出了有效提高TiO₂光催化性能的研究方向，并对未来进行了展望。

关键词: 二氧化钛, 光催化剂, 异质结, 纳米材料, 环境

CLC Number:

TQ134.1

LIN Yijie, QIAO Peng, LI Xinrui, ZHANG Hongbin, WANG Xueqin. Construction and application of heterostructures of photocatalyst TiO₂ nanomaterials[J]. Chemical Industry and Engineering Progress, 2025, 44(S1): 159-177.

林已杰, 乔鹏, 李心睿, 张宏斌, 王雪芹. TiO₂纳米光催化剂的异质结构建策略与应用研究进展[J]. 化工进展, 2025, 44(S1): 159-177.

Figures/Tables 19

References 128

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异质结	制备方法	禁带宽度E_g/eV	应用	活性效果	参考文献
TiO₂/UiO-66-NH₂	溶剂热法	2.72	光解水制氢	产氢速率比原始TiO₂提高了3.2倍	[34]
In₂O₃/TiO₂	浸渍法	2.19	有机污染物降解	氧化Hg⁰的光催化效率达到61.1%	[39]
TiO₂/ZnIn₂S₄/Co-Pi	水热法	2.55	光解水制氢	光电流密度达5.05mA/cm²，是原始TiO₂的4.8倍	[40]
TiO₂/SrTiO₃	水热法	2.57	光解水制氢	可见光下产氢速率达807.7μmol/(h·g)，比纯TiO₂纳米管高26倍	[41]
C-TiO₂/CoTiO₃	直接煅烧法	2.25	有机污染物降解	可见光下2h内降解99.6％环丙沙星	[42]
SnS₂/H-TiO₂	化学气相沉积法	2.26	光解水制氢	光电流密度达4.0mA/cm²	[43]
TiO₂:SnO₂	水热法	2.43	有害气体的治理	氧化甲烷生成甲醇[30μmol/(cm²·h)]和乙酸[8μmol/(cm²·h)]	[44]
MoS₂/TiO₂	水热法	1.13	有机污染物降解	可见光下2h内降解98.3%四环素	[45]
Bi₂O₄/TiO₂	溶剂热法	1.94	有机污染物降解	可见光下90min降解96%甲基橙（MO）	[46]
TiO₂锐钛矿-金红石异相结	碱诱导法	2.65	光解水制氢	模拟太阳光下的产氢速率达34.35mmol/(h·g)	[47]

异质结	制备方法	禁带宽度E_g/eV	应用	活性效果	参考文献
TiO₂/UiO-66-NH₂	溶剂热法	2.72	光解水制氢	产氢速率比原始TiO₂提高了3.2倍	[34]
In₂O₃/TiO₂	浸渍法	2.19	有机污染物降解	氧化Hg⁰的光催化效率达到61.1%	[39]
TiO₂/ZnIn₂S₄/Co-Pi	水热法	2.55	光解水制氢	光电流密度达5.05mA/cm²，是原始TiO₂的4.8倍	[40]
TiO₂/SrTiO₃	水热法	2.57	光解水制氢	可见光下产氢速率达807.7μmol/(h·g)，比纯TiO₂纳米管高26倍	[41]
C-TiO₂/CoTiO₃	直接煅烧法	2.25	有机污染物降解	可见光下2h内降解99.6％环丙沙星	[42]
SnS₂/H-TiO₂	化学气相沉积法	2.26	光解水制氢	光电流密度达4.0mA/cm²	[43]
TiO₂:SnO₂	水热法	2.43	有害气体的治理	氧化甲烷生成甲醇[30μmol/(cm²·h)]和乙酸[8μmol/(cm²·h)]	[44]
MoS₂/TiO₂	水热法	1.13	有机污染物降解	可见光下2h内降解98.3%四环素	[45]
Bi₂O₄/TiO₂	溶剂热法	1.94	有机污染物降解	可见光下90min降解96%甲基橙（MO）	[46]
TiO₂锐钛矿-金红石异相结	碱诱导法	2.65	光解水制氢	模拟太阳光下的产氢速率达34.35mmol/(h·g)	[47]

异质结	制备方法	禁带宽度E_g/eV	应用	活性效果	参考文献
NiS/TiO₂	水热法	1.10	有机污染物降解	在20min内实现了98%甲基橙的降解	[51]
氧空位（OVs）-BiOCl/TiO₂-δ	溶胶-凝胶法	2.88	有机污染物降解	在可见光下表观反应速率常数（0.0636/min）是TiO₂-δ（0.0026/min）的24倍	[55]
BiOCl/TiO₂	溶剂热法	2.67	有机污染物降解	可见光下四环素降解率为82%，而诺氟沙星、环丙沙星、土霉素的降解率均在90%以上	[56]
γ-石墨炔/TiO₂	机械化学法	2.27	光解水制氢	可见光下光电流密度为1.31mA/cm，是原始TiO₂的1.7倍	[57]
TiO₂量子点（QDs）/ZnBi₂O₄	水热法	2.20	有机污染物降解	可见光下罗丹明B的降解速率常数为1022×10^-4min^-1，约为TiO₂和TiO₂ QDs的77倍和5.9倍	[58]
TiO₂纳米管阵列（NTs）/Bi₂S₃-BiOI	溶剂热法	1.38	有机污染物降解	可见光下光电流密度为2.42mA/cm²，可降解93.6%罗丹明B、85.5%甲基橙、94.9%甲基蓝和99.1% Cr(Ⅵ)	[59]
FeOOH@C/TiO₂@Fe₃O₄	水解和共沉淀法	2.40	有机污染物降解	可见光下12min内完全去除As(Ⅲ)	[60]
ZnFe₂O₄/TiO₂	溶胶-凝胶法	2.32	有机污染物降解	可见光下90min降解NH₄⁺-N 98.52%	[61]
ZnO-TiO₂	磁控溅射法	2.85	抗菌	可见光下12h的杀菌率达到99.82%	[62]

异质结	制备方法	禁带宽度E_g/eV	应用	活性效果	参考文献
NiS/TiO₂	水热法	1.10	有机污染物降解	在20min内实现了98%甲基橙的降解	[51]
氧空位（OVs）-BiOCl/TiO₂-δ	溶胶-凝胶法	2.88	有机污染物降解	在可见光下表观反应速率常数（0.0636/min）是TiO₂-δ（0.0026/min）的24倍	[55]
BiOCl/TiO₂	溶剂热法	2.67	有机污染物降解	可见光下四环素降解率为82%，而诺氟沙星、环丙沙星、土霉素的降解率均在90%以上	[56]
γ-石墨炔/TiO₂	机械化学法	2.27	光解水制氢	可见光下光电流密度为1.31mA/cm，是原始TiO₂的1.7倍	[57]
TiO₂量子点（QDs）/ZnBi₂O₄	水热法	2.20	有机污染物降解	可见光下罗丹明B的降解速率常数为1022×10^-4min^-1，约为TiO₂和TiO₂ QDs的77倍和5.9倍	[58]
TiO₂纳米管阵列（NTs）/Bi₂S₃-BiOI	溶剂热法	1.38	有机污染物降解	可见光下光电流密度为2.42mA/cm²，可降解93.6%罗丹明B、85.5%甲基橙、94.9%甲基蓝和99.1% Cr(Ⅵ)	[59]
FeOOH@C/TiO₂@Fe₃O₄	水解和共沉淀法	2.40	有机污染物降解	可见光下12min内完全去除As(Ⅲ)	[60]
ZnFe₂O₄/TiO₂	溶胶-凝胶法	2.32	有机污染物降解	可见光下90min降解NH₄⁺-N 98.52%	[61]
ZnO-TiO₂	磁控溅射法	2.85	抗菌	可见光下12h的杀菌率达到99.82%	[62]

异质结	制备方法	禁带宽度E_g/eV	应用	活性效果	文献
NCDs/TNS-001	水热法	2.32	有机污染物降解	在可见光下60min对二氯荧光素的降解率达91.5%	[69]
Bi₄Ti₃O₁₂/Bi₂O₃/Bi₁₂TiO₂₀	溶胶-凝胶法	3.18	有机污染物降解	在可见光下100min对17β-雌二醇的降解率达100%	[71]
聚（二苯基丁二烯）（PDPB）/TiO₂	原位合成法	2.32	有机污染物降解	在可见光下对罗丹明B的降解率为455.5mg/(h·g_c)	[72]
TiO₂/NiO/g-C₃N₄	浸渍法	2.73	有机污染物降解	在可见光下2h对柴油的降解率为98.94%	[73]
共价有机骨架（COF）-318-TiO₂	溶剂热法	1.41	有害气体的治理	在可见光下CO₂到CO的转换效率达69.67μmol/(h·g)	[74]
AgI/N-TiO₂	水热法	2.23	有机污染物降解	在可见光下105min对四环素的降解率达79%	[75]
TiO₂@MIL-101(Cr)	水热法	2.47	有机污染物降解	在紫外光下对甲苯去除效率比MIL-101(Cr)高23.28%，比纯TiO₂高26.88%	[76]
AgIO₄/TiO₂	声化学法	1.82	光解水制氢	在可见光下的析氢速率接近8.4mmol/(h·g)	[77]
TiO₂/PPy	物理混合法	2.94	有机污染物降解	在可见光下2h完全降解活性橙16	[78]

Construction and application of heterostructures of photocatalyst TiO₂ nanomaterials

TiO₂纳米光催化剂的异质结构建策略与应用研究进展

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异质结	制备方法	禁带宽度E_g/eV	应用	活性效果	参考文献
ZnCO₂S₄/TiO₂	溶剂热法	3.10	光解水制氢和有机污染物降解	在可见光下的析氢效率达到5580μmol/(h·g)	[82]
TiO₂/In₂S₃	静电纺丝法和水热法	1.62	生产过氧化氢	在可见光下H₂O₂的产率达376µmol/(L·h)	[84]
聚噻吩类线性共轭聚合物（PB-C）/TiO₂	溶剂热法	2.06	抗菌	在全波段白光照射20min下消除了3.86×10⁷CFU/mL的耐甲氧西林金黄色葡萄球菌	[85]
In₂S₃/TiO₂	一锅水热法	2.43	有机污染物降解	在可见光下对四环素的降解率达97.3%	[86]
CeO₂/TiO₂	溶剂热法	2.32	有机污染物降解	在可见光下降解盐酸四环素的反应速率常数为0.01525min^-1，分别为TiO₂和CeO₂的1.04倍和1.81倍	[87]
TiO₂/Mn_0.2Cd_0.8S	水热法	1.88	光解水制氢	在可见光下的析氢速率达到3197μmol/(h·g)	[88]
C₃N₅/TiO₂	水热法	2.67	有机污染物降解	在可见光下降解加替沙星的反应速率常数为0.0252min^-1，是纯TiO的1.85倍	[89]
Cu-卟啉/TiO₂	溶剂热	1.27	有害气体的治理	分别在可见光和太阳光照射下还原CO₂，释放CO的速率分别为56μmol/(h·g)和73μmol/(h·g)	[90]

异质结	制备方法	产氢效果	参考文献
黑磷/TiO₂	溶剂热法	可见光下139.50μmol/(h·g)	[116]
PDBCOOH/TiO₂	共价锚定法	可见光下11.9mmol/(h·g)	[117]
TiO₂的锐钛矿-金红石异质结	碱诱导法	模拟太阳光下34.35mmol/(h·g)	[47]
TiO₂/BiVO₄	脉冲激光沉积法	可见光下14.2μmol/(cm·h)	[118]
TiO₂-MoS₂-CdS	沉积法	模拟太阳光下328μmol/(h·g)	[119]

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