半导体光催化剂BiOCl异质结的构建及应用

doi:10.16085/j.issn.1000-6613.2022-0879

摘要/Abstract

摘要：

氯氧化铋（BiOCl）半导体因其独特的层状结构和可调控的电子结构，而在光催化解决环境问题和能源问题领域备受关注。为了提高BiOCl对太阳光的利用率、抑制光生电子-空穴对的高复合率和增强光电子的还原能力等，研究人员对此作出了巨大的努力。其中，构建异质结是最有效的削弱这些缺陷的方法之一。本文主要综述了Z-型、Ⅱ-型、p-n结以及S-型四类异质结的电荷传递机理以及重点介绍了一些具有优异光催化性能的BiOCl异质结。同时，对一些异质结的光催化降解性能进行了比较分析。其中，S型异质结不仅具有高效的电荷分离能力，还有强的氧化还原能力，因此其表现出优异的光催化性能。此外，本文还简述了BiOCl异质结在降解有机污染物、还原CO₂、还原重金属和分解H₂O等方面的应用。总结了当前BiOCl异质结遇到的一些问题。最后针对BiOCl异质结的构效关系、合成复杂等问题，提出了计算机模拟、载体负载、新技术开发的发展方向。

关键词: 氯氧化铋, 异质结, 光生电子-空穴对, 光催化剂, 半导体

Abstract:

Bismuth oxychloride semiconductor has attracted tremendous attention in the field of photocatalysis for solving environmental and energy issues due to its unique layered structure and adjustable electronic structure. The researchers have made much efforts that in order to improving the utilization rate of BiOCl for sunlight, overcoming the drawback of the high recombination rates of photogenerated electron-hole pairs, enhancing the reduction ability of photoelectrons and so on. Among them the construction of heterojunction is one of the most effective ways to reduce these drawbacks. In this article, the charge transfer mechanism in 4 junction systems, Z-scheme, Ⅱ-type, p-n junction and S-scheme, are summarized. Meanwhile, they are highlighted some BiOCl heterojunctions of excellently photocatalytic performance. At the same time, the photocatalytic degradation performance is compared and analyzed for some heterojunctions. The S-scheme heterojunctions achieved high-effectively charge separation and strong photo-redox ability which resulted in exhibited excellently photocatalytic performance. In addition, the application of BiOCl heterojunctions in the degradation of organic pollutants, reduction of CO₂, reduction of heavy metals and splitting water etc. are introduced. Some problems of BiOCl heterojunction are summed up. Finally, in view of the BiOCl heterojunctions of structure-function relationship and complex synthesis etc., the development trend in computer simulation, carrier load and development of new technology is put forward.

Key words: bismuth oxychloride, heterojunction, photogenerated electron-hole pairs, photocatalyst, semiconductor

中图分类号:

TQ426

胥生元, 郝玮, 王杰, 高文生, 谢克锋. 半导体光催化剂BiOCl异质结的构建及应用[J]. 化工进展, 2023, 42(3): 1493-1507.

XU Shengyuan, HAO Wei, WANG Jie, GAO Wensheng, XIE Kefeng. Construction and application of BiOCl heterojunction as semiconductor photocatalyst[J]. Chemical Industry and Engineering Progress, 2023, 42(3): 1493-1507.

图/表 9

图1 BiOCl异质结的类型

表1 Z-型BiOCl异质结的构建总结

异质结	制备方法	制备过程	氧化与还原反应能带与最大吸收波长	文献
CdS/BiOCl	水热法	将CdS溶于水中，超声10min，然后在溶液中加入0.1mmol BNH^①和KCl，之后把混合物转移至反应釜，在180℃下反应24h	E $C B ⊖$ =-0.46eV； E $V B ⊖$ =3.47eV	[47]
CdS/CQDs^②/BiOCl	区域沉积法	将CdS量子点溶于水中，超声15min，同时，将0.5g CQDs/BiOCl分散到水中，然后将它们混合，搅拌，离心，洗涤，干燥，最后在250℃马弗炉中加热1h	E $C B ⊖$ =-0.97eV； E $V B ⊖$ =3.65eV	[66]
Fe₃O₄/BiOCl/BiOI	溶剂热法	将NaCl和NaI加入到BNH溶液中，再把0.28mmol Fe₃O₄粉末分散到混合液中，最后将混合液转移到反应釜中，并在160℃下反应12h	E $C B ⊖$ =-0.54eV； E $V B ⊖$ =3.75eV； 628nm	[67]
2D^③/2DCu₂WS₄/BiOCl	混合溶剂法	将BiOCl和Cu₂WS₄溶液混合，超声3h，搅拌并使之均匀分散，然后，离心，洗涤，在60℃下干燥，即得到产物Cu₂WS₄/BiOCl	E $C B ⊖$ =-1.91eV； E $V B ⊖$ =1.67eV	[68]
2D/2DBiOCl/K⁺CNO^④	水热法	将K⁺CNO纳米片、0.1mmol BNH和0.1mmol KCl通过搅拌和超声溶于水中，然后把混合物转移到反应釜中，在160℃加热24h	E $C B ⊖$ =-0.84eV； E $V B ⊖$ =3.55eV	[69]
BiOI/BiOCl/NFs^⑤	溶剂热法	将KCl、KI和BNH溶于EG^⑥，然后加入PAN^⑦纤维，之后把混合液全部转移至反应釜，并在160℃下反应10h	E $C B ⊖$ =-0.68eV； E $V B ⊖$ =3.71eV	[70]
BiOI/BiOCl	水热法	将[PrMIm]I^⑧溶于乙酸，然后再加入0.02mol BNH并搅拌溶解，之后加入0.02mol KCl，搅拌1h。最后将悬浮液转移至反应釜，并在180℃下反应24h	E $C B ⊖$ =-0.56eV； E $V B ⊖$ =3.47eV； 700nm	[71]
OVs-Mo₂S₃/BiOCl	原位模板法	将Mo₂S₃溶于EG中，然后加入5mL KCl乙二醇溶液（20g/L）和5mL BNH乙二醇溶液（48.5g/L）。将混合溶液放入微波反应器中，在160℃下反应15min	E $C B ⊖$ =-0.54eV； E $V B ⊖$ =3.75eV	[48]
TiO₂(B)^⑨/BiOCl_0.7I_0.3-PVP	水浴法	将0.267g TiO₂(B)加入到溶有0.5g PVP^⑩、0.007mol KCl、0.003mol KI和0.01mol BNH的水溶液中，搅拌0.5h，然后将pH调至9左右，待反应1h后，离心、洗涤和干燥	E $C B ⊖$ =-2.41eV； E $V B ⊖$ =2.62eV	[72]
Ag/BiOCl/AgIO₃	光还原法	0.3g BiOCl溶于水中，搅拌，并用350W氙灯照射30min。然后加入0.03g AgNO₃和一定量的NaIO₃，再照射2.5h得到沉淀，洗涤，干燥后即得到Ag/BiOCl/AgIO₃	E $C B ⊖$ =-2.04eV； E $V B ⊖$ =3.84eV	[46]
g-C₃N_4-_x /BiOCl/WO_2.92	溶剂热法	WCl₆溶于乙醇并搅拌。然后将0.3g g-C₃N_4-_x 分散到乙醇溶液中，最后加入NaBiO₃。将混合液搅拌后转移至反应釜中，在160℃下反应12h		[73]
Mn₃O₄/BiOCl	水热法	4.85g BNH溶于硝酸溶液中，待分散均匀后，加入10mL、0.25mol/L MnCl₂，然后用NaOH将pH调至12，最后将混合溶液转移至反应釜中，并在180℃下反应24h	E $C B ⊖$ =-0.64eV； E $V B ⊖$ =3.61eV	[74]
2D/2D BiOCl/g-C₃N₄	水热法	将0.486g BNH溶于25mL（0.1mol/L）甘露醇中，搅拌，并加入饱和NaCl。然后把g-C₃N₄均匀分散至混合液中，将混合溶液转移至反应釜，并在160℃下反应3h	E $C B ⊖$ =-1.01eV； E $V B ⊖$ =3.43eV	[75]
OVs-BiOCl/BiPO₄	溶剂热法	在0.005mol/L的H₃PO₄中加入0.13g BiOCl-OVs，搅拌1.5h，并超声10min，最后，收集沉淀，并干燥	E $C B ⊖$ =-0.65eV； E $V B ⊖$ =3.55eV	[76]
Cd/CdS/BiOCl	—	将3mmol BNH溶于50mL含5mL饱和NaCl的乙醇中。同时，将3mmol柠檬酸、3mL HNO₃和Cd/CdS溶于乙醇溶液中，最后将沉淀物质干燥		[77]

表1 Z-型BiOCl异质结的构建总结

异质结	制备方法	制备过程	氧化与还原反应能带与最大吸收波长	文献
CdS/BiOCl	水热法	将CdS溶于水中，超声10min，然后在溶液中加入0.1mmol BNH^①和KCl，之后把混合物转移至反应釜，在180℃下反应24h	E $C B ⊖$ =-0.46eV； E $V B ⊖$ =3.47eV	[47]
CdS/CQDs^②/BiOCl	区域沉积法	将CdS量子点溶于水中，超声15min，同时，将0.5g CQDs/BiOCl分散到水中，然后将它们混合，搅拌，离心，洗涤，干燥，最后在250℃马弗炉中加热1h	E $C B ⊖$ =-0.97eV； E $V B ⊖$ =3.65eV	[66]
Fe₃O₄/BiOCl/BiOI	溶剂热法	将NaCl和NaI加入到BNH溶液中，再把0.28mmol Fe₃O₄粉末分散到混合液中，最后将混合液转移到反应釜中，并在160℃下反应12h	E $C B ⊖$ =-0.54eV； E $V B ⊖$ =3.75eV； 628nm	[67]
2D^③/2DCu₂WS₄/BiOCl	混合溶剂法	将BiOCl和Cu₂WS₄溶液混合，超声3h，搅拌并使之均匀分散，然后，离心，洗涤，在60℃下干燥，即得到产物Cu₂WS₄/BiOCl	E $C B ⊖$ =-1.91eV； E $V B ⊖$ =1.67eV	[68]
2D/2DBiOCl/K⁺CNO^④	水热法	将K⁺CNO纳米片、0.1mmol BNH和0.1mmol KCl通过搅拌和超声溶于水中，然后把混合物转移到反应釜中，在160℃加热24h	E $C B ⊖$ =-0.84eV； E $V B ⊖$ =3.55eV	[69]
BiOI/BiOCl/NFs^⑤	溶剂热法	将KCl、KI和BNH溶于EG^⑥，然后加入PAN^⑦纤维，之后把混合液全部转移至反应釜，并在160℃下反应10h	E $C B ⊖$ =-0.68eV； E $V B ⊖$ =3.71eV	[70]
BiOI/BiOCl	水热法	将[PrMIm]I^⑧溶于乙酸，然后再加入0.02mol BNH并搅拌溶解，之后加入0.02mol KCl，搅拌1h。最后将悬浮液转移至反应釜，并在180℃下反应24h	E $C B ⊖$ =-0.56eV； E $V B ⊖$ =3.47eV； 700nm	[71]
OVs-Mo₂S₃/BiOCl	原位模板法	将Mo₂S₃溶于EG中，然后加入5mL KCl乙二醇溶液（20g/L）和5mL BNH乙二醇溶液（48.5g/L）。将混合溶液放入微波反应器中，在160℃下反应15min	E $C B ⊖$ =-0.54eV； E $V B ⊖$ =3.75eV	[48]
TiO₂(B)^⑨/BiOCl_0.7I_0.3-PVP	水浴法	将0.267g TiO₂(B)加入到溶有0.5g PVP^⑩、0.007mol KCl、0.003mol KI和0.01mol BNH的水溶液中，搅拌0.5h，然后将pH调至9左右，待反应1h后，离心、洗涤和干燥	E $C B ⊖$ =-2.41eV； E $V B ⊖$ =2.62eV	[72]
Ag/BiOCl/AgIO₃	光还原法	0.3g BiOCl溶于水中，搅拌，并用350W氙灯照射30min。然后加入0.03g AgNO₃和一定量的NaIO₃，再照射2.5h得到沉淀，洗涤，干燥后即得到Ag/BiOCl/AgIO₃	E $C B ⊖$ =-2.04eV； E $V B ⊖$ =3.84eV	[46]
g-C₃N_4-_x /BiOCl/WO_2.92	溶剂热法	WCl₆溶于乙醇并搅拌。然后将0.3g g-C₃N_4-_x 分散到乙醇溶液中，最后加入NaBiO₃。将混合液搅拌后转移至反应釜中，在160℃下反应12h		[73]
Mn₃O₄/BiOCl	水热法	4.85g BNH溶于硝酸溶液中，待分散均匀后，加入10mL、0.25mol/L MnCl₂，然后用NaOH将pH调至12，最后将混合溶液转移至反应釜中，并在180℃下反应24h	E $C B ⊖$ =-0.64eV； E $V B ⊖$ =3.61eV	[74]
2D/2D BiOCl/g-C₃N₄	水热法	将0.486g BNH溶于25mL（0.1mol/L）甘露醇中，搅拌，并加入饱和NaCl。然后把g-C₃N₄均匀分散至混合液中，将混合溶液转移至反应釜，并在160℃下反应3h	E $C B ⊖$ =-1.01eV； E $V B ⊖$ =3.43eV	[75]
OVs-BiOCl/BiPO₄	溶剂热法	在0.005mol/L的H₃PO₄中加入0.13g BiOCl-OVs，搅拌1.5h，并超声10min，最后，收集沉淀，并干燥	E $C B ⊖$ =-0.65eV； E $V B ⊖$ =3.55eV	[76]
Cd/CdS/BiOCl	—	将3mmol BNH溶于50mL含5mL饱和NaCl的乙醇中。同时，将3mmol柠檬酸、3mL HNO₃和Cd/CdS溶于乙醇溶液中，最后将沉淀物质干燥		[77]

表2 Ⅱ-型BiOCl异质结的构建总结

异质结	制备方法	制备过程	氧化与还原反应能带与最大吸收波长	文献
BiOCl/BOB^①	溶剂热法	将1.40g BNH均匀分散在EG^②中，然后加入0.75g BOB，并超声。之后在溶液中加入0.17g NaCl，并超声1h。最后将混合物转移到反应釜，在150℃下反应12h	E $C B ⊖$ =0.64eV； E $V B ⊖$ =3.20eV	[79]
1D-Bi₂O₂CO₃/BiOCl	水热法	将Bi₂O₂CO₃多孔纳米棒均匀分散到CH₂Cl₂中，并搅拌均匀，然后将混合物转移至反应釜，并在160℃下反应12h	E $C B ⊖$ =-0.53eV； E $V B ⊖$ =1.78eV	[80]
Ag/BiOCl/AgI	光还原法	Ag/BiOCl/AgIO₃在光催化降解过程中AgIO₃被还原为AgI，从而形成Ⅱ-型Ag/BiOCl/AgI	E $C B ⊖$ =-0.40eV； E $V B ⊖$ =1.30eV	[46]
FeWO₄/BiOCl	溶剂热法	把1mmol BNH溶于EG，再加入1mmol KCl，并将其搅拌均匀，然后加入1mmol溶于EG的FeWO₄。最后将混合物转移到反应釜中，在160℃下反应12h	E $C B ⊖$ =-0.20eV； E $V B ⊖$ =2.20eV 800nm	[81]
3D BiO₇I/BiOCl	原位共沉淀法	将200mg BiO₇I分散在EG中，并超声20min，然后在溶液中加入0.248g BNH，并搅拌均匀，再加入等物质的量的KCl溶液，搅拌1h，最后将混合物转移至反应釜，并在160℃下反应12h	E $C B ⊖$ =-0.15eV； E $V B ⊖$ =2.52eV； 482nm	[82]
2D/2D BiOCl/HTN7^③	水热法	在HTN7悬浮液中加入0.2mmol BNH和0.2mmol KCl，连续搅拌。然后，将混合物转移到反应釜中，在160℃下加热24h	E $C B ⊖$ =-0.53eV； E $V B ⊖$ =2.52eV	[83]
BiOCl/HTN5^④	水热法	在HTN5悬浮液中加入0.1mmol BNH和0.1mmol KCl，并超声，然后，将混合物转移到反应釜中，在160℃下加热24h	E $C B ⊖$ =-0.57eV； E $V B ⊖$ =2.28eV；	[84]
BiOCl/Bi₃NbO₇	原位化学刻蚀法	将0.2g Bi₃NbO₇溶于5.5mL乙醇中，然后缓慢加入0.5mL HCl，待反应结束后，收集沉淀，并将其洗涤，干燥	E $C B ⊖$ =-0.38eV； E $V B ⊖$ =2.16eV； 500nm	[44]
BiOCl/BTO^⑤	原位水热法	将BiOCl NFs、BNH和C₁₆H₃₆O₄Ti超声均匀分散在水中，然后转移至反应釜中，在160℃下反应12h	E^θ_CB=-0.35eV； E $V B ⊖$ =2.20eV	[85]
BiOI/BiOCl	无模板共沉淀法	将5mmol BNH溶于水中，搅拌均匀，然后加入KCl和KI，搅拌5h，洗涤，离心，干燥，即得到BiOI/BiOCl		[86]
Nb₂O₅/BiOCl	水热法	将0.5g BiOCl分散于水中，然后加入Nb₂O₅，搅拌24h，离心，干燥，研磨，即制得Nb₂O₅/BiOCl样品	E $C B ⊖$ =-0.87eV； E $V B ⊖$ =1.99eV	[87]
BiOCl/In₂S₃	研磨法	将BiOCl和In₂S₃混合并置于研钵中，快速研磨20min，得到复合光催化剂BiOCl/In₂S₃	E $C B ⊖$ =-0.99eV； E $V B ⊖$ =0.77eV； 900nm	[88]
g-C₃N₄/BiOCl	水热法	将BNH和KCl溶于EG中，然后在溶液中加入g-C₃N₄，并超声30min，再将含0.1g Na₂CO₃的溶液加入EG中，最后将混合物转移至反应釜中，并在130℃下反应12h	E $C B ⊖$ =-0.77eV； E $V B ⊖$ =0.91eV； 800nm	[89]

表2 Ⅱ-型BiOCl异质结的构建总结

异质结	制备方法	制备过程	氧化与还原反应能带与最大吸收波长	文献
BiOCl/BOB^①	溶剂热法	将1.40g BNH均匀分散在EG^②中，然后加入0.75g BOB，并超声。之后在溶液中加入0.17g NaCl，并超声1h。最后将混合物转移到反应釜，在150℃下反应12h	E $C B ⊖$ =0.64eV； E $V B ⊖$ =3.20eV	[79]
1D-Bi₂O₂CO₃/BiOCl	水热法	将Bi₂O₂CO₃多孔纳米棒均匀分散到CH₂Cl₂中，并搅拌均匀，然后将混合物转移至反应釜，并在160℃下反应12h	E $C B ⊖$ =-0.53eV； E $V B ⊖$ =1.78eV	[80]
Ag/BiOCl/AgI	光还原法	Ag/BiOCl/AgIO₃在光催化降解过程中AgIO₃被还原为AgI，从而形成Ⅱ-型Ag/BiOCl/AgI	E $C B ⊖$ =-0.40eV； E $V B ⊖$ =1.30eV	[46]
FeWO₄/BiOCl	溶剂热法	把1mmol BNH溶于EG，再加入1mmol KCl，并将其搅拌均匀，然后加入1mmol溶于EG的FeWO₄。最后将混合物转移到反应釜中，在160℃下反应12h	E $C B ⊖$ =-0.20eV； E $V B ⊖$ =2.20eV 800nm	[81]
3D BiO₇I/BiOCl	原位共沉淀法	将200mg BiO₇I分散在EG中，并超声20min，然后在溶液中加入0.248g BNH，并搅拌均匀，再加入等物质的量的KCl溶液，搅拌1h，最后将混合物转移至反应釜，并在160℃下反应12h	E $C B ⊖$ =-0.15eV； E $V B ⊖$ =2.52eV； 482nm	[82]
2D/2D BiOCl/HTN7^③	水热法	在HTN7悬浮液中加入0.2mmol BNH和0.2mmol KCl，连续搅拌。然后，将混合物转移到反应釜中，在160℃下加热24h	E $C B ⊖$ =-0.53eV； E $V B ⊖$ =2.52eV	[83]
BiOCl/HTN5^④	水热法	在HTN5悬浮液中加入0.1mmol BNH和0.1mmol KCl，并超声，然后，将混合物转移到反应釜中，在160℃下加热24h	E $C B ⊖$ =-0.57eV； E $V B ⊖$ =2.28eV；	[84]
BiOCl/Bi₃NbO₇	原位化学刻蚀法	将0.2g Bi₃NbO₇溶于5.5mL乙醇中，然后缓慢加入0.5mL HCl，待反应结束后，收集沉淀，并将其洗涤，干燥	E $C B ⊖$ =-0.38eV； E $V B ⊖$ =2.16eV； 500nm	[44]
BiOCl/BTO^⑤	原位水热法	将BiOCl NFs、BNH和C₁₆H₃₆O₄Ti超声均匀分散在水中，然后转移至反应釜中，在160℃下反应12h	E^θ_CB=-0.35eV； E $V B ⊖$ =2.20eV	[85]
BiOI/BiOCl	无模板共沉淀法	将5mmol BNH溶于水中，搅拌均匀，然后加入KCl和KI，搅拌5h，洗涤，离心，干燥，即得到BiOI/BiOCl		[86]
Nb₂O₅/BiOCl	水热法	将0.5g BiOCl分散于水中，然后加入Nb₂O₅，搅拌24h，离心，干燥，研磨，即制得Nb₂O₅/BiOCl样品	E $C B ⊖$ =-0.87eV； E $V B ⊖$ =1.99eV	[87]
BiOCl/In₂S₃	研磨法	将BiOCl和In₂S₃混合并置于研钵中，快速研磨20min，得到复合光催化剂BiOCl/In₂S₃	E $C B ⊖$ =-0.99eV； E $V B ⊖$ =0.77eV； 900nm	[88]
g-C₃N₄/BiOCl	水热法	将BNH和KCl溶于EG中，然后在溶液中加入g-C₃N₄，并超声30min，再将含0.1g Na₂CO₃的溶液加入EG中，最后将混合物转移至反应釜中，并在130℃下反应12h	E $C B ⊖$ =-0.77eV； E $V B ⊖$ =0.91eV； 800nm	[89]

表3 p-n BiOCl异质结的构建总结

异质结	制备方法	制备过程	氧化与还原反应能带与最大吸收波长	文献
0D/2D CuO/BiOCl	原位生长法	BiOCl纳米片和0.05g Cu(CH₃COO)₂·5H₂O加入到含50mL DMF^①的锥形瓶中，并搅拌，然后在90℃水浴中，搅拌4h，并离心	E $C B ⊖$ =0.26eV； E $V B ⊖$ =1.55eV	[91]
OVs-BiOCl/TiO_2-_δ	一锅沉积法	将NaCl/TiO_2-_δ 和BNH溶于pH=10的NaOH溶液中，然后搅拌24h，即得到OVs-BiOCl/TiO_2-_δ	E $C B ⊖$ =-0.47eV； E $V B ⊖$ =2.41eV	[92]
3D/2D BiVO₄/BiOCl	原位沉积法	将BiVO₄分散在水中，再将含0.1mmol BNH的EG溶液转移至BiVO₄悬浮液中，并滴加盐酸，搅拌5h，离心，洗涤，干燥		[93]
CuBi₂O₄/BiOCl	一锅水热法	将BNH、Cu(NO₃)₃·3H₂O和NaOH溶于水中，然后将BNH和KCl混合后，加入水溶液中，并搅拌，最后将混合物转移反应釜中，在180℃下反应24h	E $C B ⊖$ =-0.23eV； E $V B ⊖$ =1.40eV	[56]
{110}BiOCl/ZnO	溶剂热法	分别将6mmol六亚甲基四胺和Zn(CH₃COO)₂·3H₂O溶于水，然后混合均匀，再加入BiOCl，并搅匀，最后将混合物转移至反应釜，并在90℃下反应6h		[94]
SCIs^②-BiOCl/ZnO	一锅水热法	将ZnCl₂、Na₂SnO₃·3H₂O和BNH分别溶于水中，然后混合并搅拌30min，再将混合物转移至反应釜，并在200℃下反应12h	E $C B ⊖$ =-0.34eV； E $V B ⊖$ =2.65eV	[43]
BiOCl/ZnO	水热法	在含3mmol Zn(NO₃)₃·6H₂O的溶液中加入NaOH，生成白色沉淀后，加入KCl，并搅拌，然后加入BNH，最后将混合溶液转移至反应釜中，在100℃下反应2h		[95]
OVs-BiOCl/g-C₃N₄	微波辅助法	分别将g-C₃N₄、KCl和BNH溶于EG中，然后混合搅拌3min，微波加热至160℃下反应15min	E $C B ⊖$ =-0.66eV； E $V B ⊖$ =1.40eV； 473nm	[96]
α-Fe₂O₃/BiOCl	—	在CH₃COOH中加入0.182g BNH，再加入α-Fe₂O₃，搅拌30min，然后加入KCl溶液，搅拌，陈化3h，过滤，洗涤，干燥		[97]
FeVO₄@BiOCl	水热法	将1mmol BNH和1mmol KCl溶于水中，连续搅拌，然后将FeVO₄加入溶液中，最后将悬浮液转移至反应釜中，在160℃下反应18h	650nm	[98]
BiPO₄/BiOCl	原位化学转化法	2.6g BiOCl溶于乙醇中，超声15min，然后加入H₃PO₄，并搅拌均匀，离心即得到BiPO₄/BiOCl		[99]
BiOCl@WO₃	水热法	分别将WO₃和BNH分散在乙醇中，搅拌均匀后混合，然后加入KCl，搅拌，最后将混合物转移至反应釜中，在160℃下反应20h	E $C B ⊖$ =0.67eV； E $V B ⊖$ =2.91eV	[100]
BiOCl/TiO₂/CNFs^③	溶剂热法	将5mmol Bi(NO₃)₃和KCl分别溶于EG中，再将它们溶于乙醇中，并搅拌1h，然后将0.015g TiO₂/CNFs加入混合溶液中浸泡，最后经溶剂热处理，洗涤、过滤、干燥得到复合材料	E $C B ⊖$ =0.22eV； E $V B ⊖$ =2.89eV；	[101]
0D/2D CsPbBr₃/BiOCl	—	100mg BiOCl超声分散于乙酸乙酯中，然后加入15mL CsPbBr₃溶液，超声30min，并搅拌30min，干燥，得到CsPbBr₃/BiOCl	E $C B ⊖$ =0.53eV； E $V B ⊖$ =1.50eV	[102]

表3 p-n BiOCl异质结的构建总结

异质结	制备方法	制备过程	氧化与还原反应能带与最大吸收波长	文献
0D/2D CuO/BiOCl	原位生长法	BiOCl纳米片和0.05g Cu(CH₃COO)₂·5H₂O加入到含50mL DMF^①的锥形瓶中，并搅拌，然后在90℃水浴中，搅拌4h，并离心	E $C B ⊖$ =0.26eV； E $V B ⊖$ =1.55eV	[91]
OVs-BiOCl/TiO_2-_δ	一锅沉积法	将NaCl/TiO_2-_δ 和BNH溶于pH=10的NaOH溶液中，然后搅拌24h，即得到OVs-BiOCl/TiO_2-_δ	E $C B ⊖$ =-0.47eV； E $V B ⊖$ =2.41eV	[92]
3D/2D BiVO₄/BiOCl	原位沉积法	将BiVO₄分散在水中，再将含0.1mmol BNH的EG溶液转移至BiVO₄悬浮液中，并滴加盐酸，搅拌5h，离心，洗涤，干燥		[93]
CuBi₂O₄/BiOCl	一锅水热法	将BNH、Cu(NO₃)₃·3H₂O和NaOH溶于水中，然后将BNH和KCl混合后，加入水溶液中，并搅拌，最后将混合物转移反应釜中，在180℃下反应24h	E $C B ⊖$ =-0.23eV； E $V B ⊖$ =1.40eV	[56]
{110}BiOCl/ZnO	溶剂热法	分别将6mmol六亚甲基四胺和Zn(CH₃COO)₂·3H₂O溶于水，然后混合均匀，再加入BiOCl，并搅匀，最后将混合物转移至反应釜，并在90℃下反应6h		[94]
SCIs^②-BiOCl/ZnO	一锅水热法	将ZnCl₂、Na₂SnO₃·3H₂O和BNH分别溶于水中，然后混合并搅拌30min，再将混合物转移至反应釜，并在200℃下反应12h	E $C B ⊖$ =-0.34eV； E $V B ⊖$ =2.65eV	[43]
BiOCl/ZnO	水热法	在含3mmol Zn(NO₃)₃·6H₂O的溶液中加入NaOH，生成白色沉淀后，加入KCl，并搅拌，然后加入BNH，最后将混合溶液转移至反应釜中，在100℃下反应2h		[95]
OVs-BiOCl/g-C₃N₄	微波辅助法	分别将g-C₃N₄、KCl和BNH溶于EG中，然后混合搅拌3min，微波加热至160℃下反应15min	E $C B ⊖$ =-0.66eV； E $V B ⊖$ =1.40eV； 473nm	[96]
α-Fe₂O₃/BiOCl	—	在CH₃COOH中加入0.182g BNH，再加入α-Fe₂O₃，搅拌30min，然后加入KCl溶液，搅拌，陈化3h，过滤，洗涤，干燥		[97]
FeVO₄@BiOCl	水热法	将1mmol BNH和1mmol KCl溶于水中，连续搅拌，然后将FeVO₄加入溶液中，最后将悬浮液转移至反应釜中，在160℃下反应18h	650nm	[98]
BiPO₄/BiOCl	原位化学转化法	2.6g BiOCl溶于乙醇中，超声15min，然后加入H₃PO₄，并搅拌均匀，离心即得到BiPO₄/BiOCl		[99]
BiOCl@WO₃	水热法	分别将WO₃和BNH分散在乙醇中，搅拌均匀后混合，然后加入KCl，搅拌，最后将混合物转移至反应釜中，在160℃下反应20h	E $C B ⊖$ =0.67eV； E $V B ⊖$ =2.91eV	[100]
BiOCl/TiO₂/CNFs^③	溶剂热法	将5mmol Bi(NO₃)₃和KCl分别溶于EG中，再将它们溶于乙醇中，并搅拌1h，然后将0.015g TiO₂/CNFs加入混合溶液中浸泡，最后经溶剂热处理，洗涤、过滤、干燥得到复合材料	E $C B ⊖$ =0.22eV； E $V B ⊖$ =2.89eV；	[101]
0D/2D CsPbBr₃/BiOCl	—	100mg BiOCl超声分散于乙酸乙酯中，然后加入15mL CsPbBr₃溶液，超声30min，并搅拌30min，干燥，得到CsPbBr₃/BiOCl	E $C B ⊖$ =0.53eV； E $V B ⊖$ =1.50eV	[102]

表4 S-型BiOCl异质结的构建总结

异质结	制备方法	制备过程	氧化与还原反应能带与最大吸收波长	文献
0D/3D Ta₃N₅/BiOCl	溶剂热法	将BNH溶于EG中，超声后再加入Ta₃N₅，并超声1h，然后加入KCl，并搅拌1h，最后将混合物转移至反应釜，并在160℃下反应12h	E $C B ⊖$ =-0.66eV； E $V B ⊖$ =3.26eV； 800nm	[54]
In₂O₃/BiOCl	熔盐法	将KNO₃和LiNO₃充分研磨，然后在KNO₃-LiNO₃中加入KCl、BNH和In₂O₃，研磨1h。随后将混合物放入坩埚中，在350℃的马弗炉中烧3h，冷却后，洗涤，最后在90℃下干燥8h	E $C B ⊖$ =-0.70eV； E $V B ⊖$ =3.05eV	[103]
CdS/{001}BiOCl	化学沉积法	将Cd(CH₃COO)₂·2H₂O溶于水中，再将200mg（001）BiOCl均匀分散于溶液中，然后加入硫脲，并搅拌30min，最后在90℃下加热2.5h	E $C B ⊖$ =-0.90eV； E $V B ⊖$ =2.83eV	[104]
BBOC/MIS^①	原位水热法	将Bi-BiOCl分散在乙醇和水的混合溶液中，超声，搅拌，然后加入MgCl₂·6H₂O、InCl₃·4H₂O和TAA^②，并搅拌30min，最后将混合物转移到反应釜，并在180℃下反应24h	E $C B ⊖$ =-0.55eV； E $V B ⊖$ =3.92eV 697nm	[105]
BOCl/CBO	溶剂热法	将BNH溶于EG中，再加入0.2g CBO，混合搅拌，然后加入KCl，搅拌均匀后，将混合物转移至反应釜，在160℃下反应12h	E $C B ⊖$ =-0.50eV； E $V B ⊖$ =3.12eV	[106]
0D/2D Cu₂O/BiOCl	水热法	将BiOCl粉末分散在含5mmol CuCl₂的水中，然后加入0.5mol/L NaOH溶液，并搅拌，再加入0.1mol/L维生素C溶液，待反应30min后，洗涤，干燥，即得到Cu₂O/BiOCl	E $C B ⊖$ =-0.91eV； E $V B ⊖$ =2.83eV	[107]
2D/2D CIS^③/BiOCl	水热法	将BiOCl粉末分散在水中，再加入0.0076g TAA，并超声，然后加入In(NO₃)₃和Ca(NO₃)₂，并搅拌1h，最后将悬浮液转移至反应釜，并在160℃下反应12h	E $C B ⊖$ =-0.53eV； E $V B ⊖$ =1.88eV	[108]
BiOCl/CdS	水热法	将100mg BiOCl分散在水中，搅拌30min，然后加入NH₂CSNH₂和Cd(COO)₂·6H₂O，搅匀后转移至反应釜，并在120℃下反应4h	E $C B ⊖$ =-0.57eV； E $V B ⊖$ =3.39eV	[109]
BiOCl/MoSe₂	溶剂热法	将BiOCl、Na₂MoO₄·2H₂O、硒粉和NaBH₄加入体积比为1∶1的乙醇和水中，搅拌1h，然后将混合物转移至反应釜，并在180℃下反应12h	E $C B ⊖$ =-0.59eV； E $V B ⊖$ =3.51eV	[110]

表4 S-型BiOCl异质结的构建总结

异质结	制备方法	制备过程	氧化与还原反应能带与最大吸收波长	文献
0D/3D Ta₃N₅/BiOCl	溶剂热法	将BNH溶于EG中，超声后再加入Ta₃N₅，并超声1h，然后加入KCl，并搅拌1h，最后将混合物转移至反应釜，并在160℃下反应12h	E $C B ⊖$ =-0.66eV； E $V B ⊖$ =3.26eV； 800nm	[54]
In₂O₃/BiOCl	熔盐法	将KNO₃和LiNO₃充分研磨，然后在KNO₃-LiNO₃中加入KCl、BNH和In₂O₃，研磨1h。随后将混合物放入坩埚中，在350℃的马弗炉中烧3h，冷却后，洗涤，最后在90℃下干燥8h	E $C B ⊖$ =-0.70eV； E $V B ⊖$ =3.05eV	[103]
CdS/{001}BiOCl	化学沉积法	将Cd(CH₃COO)₂·2H₂O溶于水中，再将200mg（001）BiOCl均匀分散于溶液中，然后加入硫脲，并搅拌30min，最后在90℃下加热2.5h	E $C B ⊖$ =-0.90eV； E $V B ⊖$ =2.83eV	[104]
BBOC/MIS^①	原位水热法	将Bi-BiOCl分散在乙醇和水的混合溶液中，超声，搅拌，然后加入MgCl₂·6H₂O、InCl₃·4H₂O和TAA^②，并搅拌30min，最后将混合物转移到反应釜，并在180℃下反应24h	E $C B ⊖$ =-0.55eV； E $V B ⊖$ =3.92eV 697nm	[105]
BOCl/CBO	溶剂热法	将BNH溶于EG中，再加入0.2g CBO，混合搅拌，然后加入KCl，搅拌均匀后，将混合物转移至反应釜，在160℃下反应12h	E $C B ⊖$ =-0.50eV； E $V B ⊖$ =3.12eV	[106]
0D/2D Cu₂O/BiOCl	水热法	将BiOCl粉末分散在含5mmol CuCl₂的水中，然后加入0.5mol/L NaOH溶液，并搅拌，再加入0.1mol/L维生素C溶液，待反应30min后，洗涤，干燥，即得到Cu₂O/BiOCl	E $C B ⊖$ =-0.91eV； E $V B ⊖$ =2.83eV	[107]
2D/2D CIS^③/BiOCl	水热法	将BiOCl粉末分散在水中，再加入0.0076g TAA，并超声，然后加入In(NO₃)₃和Ca(NO₃)₂，并搅拌1h，最后将悬浮液转移至反应釜，并在160℃下反应12h	E $C B ⊖$ =-0.53eV； E $V B ⊖$ =1.88eV	[108]
BiOCl/CdS	水热法	将100mg BiOCl分散在水中，搅拌30min，然后加入NH₂CSNH₂和Cd(COO)₂·6H₂O，搅匀后转移至反应釜，并在120℃下反应4h	E $C B ⊖$ =-0.57eV； E $V B ⊖$ =3.39eV	[109]
BiOCl/MoSe₂	溶剂热法	将BiOCl、Na₂MoO₄·2H₂O、硒粉和NaBH₄加入体积比为1∶1的乙醇和水中，搅拌1h，然后将混合物转移至反应釜，并在180℃下反应12h	E $C B ⊖$ =-0.59eV； E $V B ⊖$ =3.51eV	[110]

图2 S-型异质结BBOC/MIS能带结构和e-迁移方式[105]

图3 g-C3N4-x /BiOCl/WO2.92异质结的光催化机理[73]

图4 可见光照射下，S-型Ta3N5/BiOCl光催化去除Cr(Ⅵ)的机理和电荷转移[54]

图5 BiOX/CuFe2O4（CFO）催化剂[127]

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