ZnSn(OH)6 基纳米材料在环境光催化中的应用

doi:10.16085/j.issn.1000-6613.2022-0646

化工进展 ›› 2023, Vol. 42 ›› Issue (2): 756-764.DOI: 10.16085/j.issn.1000-6613.2022-0646

ZnSn(OH)₆ 基纳米材料在环境光催化中的应用

陈邦富¹(), 欧阳平¹, 李宇涵¹^,²(), 段有雨³(), 董帆¹^,⁴

^1.重庆工商大学废油资源化技术与装备教育部工程技术研究中心，重庆市催化与环境新材料重点实验室，环境与资源学院，重庆 400067
^2.南昌理工学院，江西南昌 330044
^3.重庆大学物理学院，重庆 401331
^4.成都电子科技大学基础与前沿科学研究所环境与能源催化研究中心，四川成都 611731

收稿日期:2022-04-13 修回日期:2022-06-22 出版日期:2023-02-25 发布日期:2023-03-13
通讯作者: 李宇涵,段有雨
作者简介:陈邦富（1996—），男，硕士研究生，研究方向为光催化纳米复合材料。E-mail：cbf19964118@163.com。
基金资助:
国家自然科学基金青年基金(51808080);重庆市教委项目(KJQN201800826);重庆市博士后出站留渝项目

Application of ZnSn(OH)₆-based nanomaterials in environmental photocatalysis

CHEN Bangfu¹(), OUYANG Ping¹, LI Yuhan¹^,²(), DUAN Youyu³(), DONG Fan¹^,⁴

^1.Engineering Research Center for Waste Oil Recovery Technology and Equipment, Ministry of Education, Chongqing Key Laboratory of Catalysis and New Environmental Materials, School of Environment and Resources, Chongqing Technology and Business University, Chongqing 400067, China
^2.Nanchang Institute of Technology, Nanchang 330044, Jiangxi, China
^3.College of Physics, Chongqing University, Chongqing 401331, China
^4.Research Center for Environmental and Energy Catalysis, Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu 611731, Sichuan, China

Received:2022-04-13 Revised:2022-06-22 Online:2023-02-25 Published:2023-03-13
Contact: LI Yuhan, DUAN Youyu

摘要/Abstract

摘要：

本征ZnSn(OH)₆具有较宽的带隙（约4.0eV），价带和导带位置使其具有较高的氧化还原电势，有利于驱动光催化氧化还原反应，在环境净化和能源开发等领域展现出良好的应用前景。本文从ZnSn(OH)₆物理和化学性质出发，介绍了ZnSn(OH)₆晶体结构和表面结构，分析了制备方法对光催化性能的影响；基于ZnSn(OH)₆在光催化方面的应用研究，总结了ZnSn(OH)₆的改性策略，包括引入缺陷、元素掺杂、构建异质结、晶面调控；最后，重点概述了ZnSn(OH)₆基光催化材料在能源（产氢、二氧化碳还原）和环境领域（污水治理、空气净化）的应用。同时指出ZnSn(OH)₆基光催化剂在实际应用研究方面仍处于初步阶段，需要进一步探究改性策略对ZnSn(OH)₆应用需求的精准性，拓展其应用场景，为后续研究工作提供方向和思路，加速其工业化应用的进程。

关键词: ZnSn(OH)₆, 改性策略, 光催化材料, 光催化应用

Abstract:

The intrinsic ZnSn(OH)₆ has a wide band gap (about 4.0eV), and the valence band and conduction band position make it have high redox potential, which is conducive to driving the photocatalytic redox reaction. It shows a good application prospect in the fields of environmental purification and energy development. In this review, the crystal structure and surface structure of ZnSn(OH)₆ are introduced according to its physical and chemical properties. Based on the application of ZnSn(OH)₆ in photocatalysis, the modification strategies of ZnSn(OH)₆ are outlined, including defect engineering, element doping, heterojunction establishment and crystal control. Finally, the application of ZnSn(OH)₆ in energy development (hydrogen production and carbon dioxide reduction) and environmental treatment (sewage disposal and air purification) are emphasized. At the same time, it is pointed out that the practical application of ZnSn(OH)₆-based photocatalyst is still in the preliminary stage. In the future, it is necessary to further explore the accuracy of the modification strategy for ZnSn(OH)₆ application requirements, expand its application fields, provide approaches and ideas for follow-up research, and accelerate the process of its industrial application.

Key words: ZnSn(OH)₆, modified strategy, photocatalytic material, photocatalytic application

中图分类号:

O643.36

陈邦富, 欧阳平, 李宇涵, 段有雨, 董帆. ZnSn(OH)₆ 基纳米材料在环境光催化中的应用[J]. 化工进展, 2023, 42(2): 756-764.

CHEN Bangfu, OUYANG Ping, LI Yuhan, DUAN Youyu, DONG Fan. Application of ZnSn(OH)₆-based nanomaterials in environmental photocatalysis[J]. Chemical Industry and Engineering Progress, 2023, 42(2): 756-764.

图/表 10

图1 ZnSn(OH)6的晶体结构和表面结构

图2 在立方(1)和球形(2)ZnSn(OH)6上测量的EPR光谱[11]

图3 C-ZnSn(OH)6光催化剂的速率常数的柱状图[27]

图4 BiOI/ZnSn(OH)6和ZnSn(OH)6/SnO2/rGO的能带位置及光催化机理

图5 不同前体摩尔比的ZnSn(OH)6多面体的FESEM图像（SnCl4∶ZnAc2∶NaOH =1∶1∶X）和不同的面积比R对应的三维几何模型[36]

表1 部分ZnSn(OH)6基光催化剂的改性及应用案例

催化剂	改性方法	应用	测试条件	光催化性能	结论和分析	参考文献
ZnSn(OH)₆	引入缺陷	CO₂还原	300W氙气弧光灯；CO₂(99.999 %)；0.1g ZnSn(OH)₆	1h内，ZnSn(OH)₆-O_Vs-2-h CO的产率达到峰值99.175μmol/g	分子在受阻路易斯酸碱对上的异裂解加速了 $C O 2 + H 2 → C O + H 2 O$ 的光驱动反应	[37]
C-ZnSn(OH)₆	引入C 元素	苯；环己烷	紫外光；0.58% C-ZnSn(OH)₆	300min后，对苯和环己烷的光催化转化率分别高达77%和50.5%	BET表面积增大，粒径减小，增强颗粒间的界面电荷转移，光生e^--h⁺对分离效率提高	[38]
Ni/ZnSn(OH)₆	引入Ni元素	4-硝基苯胺	可见光；0.25g（质量分数0.3%）Ni/ZnSn(OH)₆；80mL 4-硝基苯胺	60min后，4-硝基苯胺的最大光催化还原效率达到100%	减小ZnSn(OH)₆的带隙［质量分数0.3% Ni/ZnSn(OH)₆带隙能量约为2.79eV］	[26]
AgI/ZnSn(OH)₆	异质结构建	罗丹明B（RhB）	可见光；AgI/ZnSn(OH)₆（AgI质量分数20%）	40min内，AgI/ZnSn(OH)₆对RhB去除率达到100%；总有机碳去除率约91%	ZnSn(OH)₆在形成的AgI/ZnSn(OH)₆体系中起到了电子陷阱的作用，促进了电子-空穴对的分离，保证了催化剂的稳定性	[3]
ZnSn(OH)₆	晶面调控	苯（C₆H₆）	4个4W UV灯（λ=254nm）；用纯氧（240mg/L±10mg/L）稀释的苯作为反应物流	25h后，C₆H₆在八面体ZnSn(OH)₆上的转换率为13mg/(L·m²)	ZnSn(OH)₆的{111}面对苯的氧化表现出比{100}面更好的光催化活性	[39]

表1 部分ZnSn(OH)6基光催化剂的改性及应用案例

催化剂	改性方法	应用	测试条件	光催化性能	结论和分析	参考文献
ZnSn(OH)₆	引入缺陷	CO₂还原	300W氙气弧光灯；CO₂(99.999 %)；0.1g ZnSn(OH)₆	1h内，ZnSn(OH)₆-O_Vs-2-h CO的产率达到峰值99.175μmol/g	分子在受阻路易斯酸碱对上的异裂解加速了 $C O 2 + H 2 → C O + H 2 O$ 的光驱动反应	[37]
C-ZnSn(OH)₆	引入C 元素	苯；环己烷	紫外光；0.58% C-ZnSn(OH)₆	300min后，对苯和环己烷的光催化转化率分别高达77%和50.5%	BET表面积增大，粒径减小，增强颗粒间的界面电荷转移，光生e^--h⁺对分离效率提高	[38]
Ni/ZnSn(OH)₆	引入Ni元素	4-硝基苯胺	可见光；0.25g（质量分数0.3%）Ni/ZnSn(OH)₆；80mL 4-硝基苯胺	60min后，4-硝基苯胺的最大光催化还原效率达到100%	减小ZnSn(OH)₆的带隙［质量分数0.3% Ni/ZnSn(OH)₆带隙能量约为2.79eV］	[26]
AgI/ZnSn(OH)₆	异质结构建	罗丹明B（RhB）	可见光；AgI/ZnSn(OH)₆（AgI质量分数20%）	40min内，AgI/ZnSn(OH)₆对RhB去除率达到100%；总有机碳去除率约91%	ZnSn(OH)₆在形成的AgI/ZnSn(OH)₆体系中起到了电子陷阱的作用，促进了电子-空穴对的分离，保证了催化剂的稳定性	[3]
ZnSn(OH)₆	晶面调控	苯（C₆H₆）	4个4W UV灯（λ=254nm）；用纯氧（240mg/L±10mg/L）稀释的苯作为反应物流	25h后，C₆H₆在八面体ZnSn(OH)₆上的转换率为13mg/(L·m²)	ZnSn(OH)₆的{111}面对苯的氧化表现出比{100}面更好的光催化活性	[39]

图6 比较不同反应条件下的析氢速率[6]

图7 暴露{100}和{111}面的SC和SO对CO2吸附量[14](SC表示立方体，AR{100}/{111}=1∶0；SO表示八面体，AR{100}/{111}=0∶1)

图8 ZnSn(OH)6基复合材料降解污染物的机理及活性图

图9 ZnSn(OH)6基复合材料光催化降解VOCs和NO机理及活性图

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ZnSn(OH)₆ 基纳米材料在环境光催化中的应用

Application of ZnSn(OH)₆-based nanomaterials in environmental photocatalysis

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