石墨烯桥联的ZnO/Ag<sub>3</sub>PO<sub>4</sub>复合材料的制备及其对环丙沙星的降解性能

杜春艳; 宋佳豪; 谭诗杨; 阳露; 张卓; 余关龙

doi:10.13801/j.cnki.fhclxb.20200909.001

石墨烯桥联的ZnO/Ag₃PO₄复合材料的制备及其对环丙沙星的降解性能

doi: 10.13801/j.cnki.fhclxb.20200909.001

杜春艳^{1, 2, ,},
宋佳豪^1,,
谭诗杨^1,,
阳露^1,,
张卓^1,,
余关龙^{1, 2,}

1.
长沙理工大学　水利工程学院，长沙 410114
2.
洞庭湖水环境治理与生态修复湖南省重点实验室，长沙 410114

基金项目: 湖南省教育厅科学研究项目(18B127；19A032；16C0060)；国家自然科学基金(51109016)

详细信息

通讯作者:
杜春艳，博士，讲师，硕士生导师，研究方向为水处理新材料　E-mail：cydu@csust.edu.cn

中图分类号: TB333
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- 被引次数: 0
出版历程
- 收稿日期: 2020-07-16
- 录用日期: 2020-08-27
- 网络出版日期: 2020-09-10
- 刊出日期: 2021-07-15

Preparation of graphene bridged ZnO/Ag₃PO₄ composite and its degradation performance for ciprofloxacin

DU Chunyan^{1, 2
, ,},
SONG Jiahao^1
,,
TAN Shiyang^1
,,
YANG Lu^1
,,
ZHANG Zhuo^1
,,
YU Guanlong^{1, 2
,}

1.
School of Hydraulic Engineering, Changsha University of Science & Technology, Changsha 410114, China
2.
Key Laboratory of Dongting Lake Aquatic Eco-Environmental Control and Restoration of Hunan Province, Changsha 410114, China

摘要

摘要: 采用沉淀沉积法制备了石墨烯桥联的ZnO/Ag₃PO₄复合光催化材料，具有优异的可见光催化性能，通过XRD、XPS、SEM、EDS、BET、FTIR、UV-Vis DRS、PL及ESR等表征手段对其晶体结构、形貌、光学性质等进行了表征及分析，并研究了不同氧化石墨烯比例的GO-ZnO/Ag₃PO₄复合材料对模拟抗生素废水环丙沙星(CIP)的光催化降解性能。由于GO及ZnO的引入，不仅增强了GO-ZnO/Ag₃PO₄对可见光吸收，且拥有了更高的电子-空穴对的分离效率。当GO与Ag₃PO₄的质量比为1%时，GO-ZnO/Ag₃PO₄显示出最佳的光催化活性，60 min可见光照后对CIP降解率可达85.3%。捕获实验表明，超氧自由基(·O₂⁻)是反应过程中的主要活性物质，ZnO与Ag₃PO₄之间形成了异质结，符合Z型电子转移机制，GO的引入进一步提高了电子的快速转移，并使Z型体系更加稳定。经过6次光催化循环，降解率依然保持在70%以上，表明GO-ZnO/Ag₃PO₄复合材料具有优异的稳定性。
- 石墨烯 /
- GO-ZnO/Ag₃PO₄ /
- 光催化 /
- 异质结 /
- 环丙沙星 /
- 复合材料
Abstract: Graphene-bridged ZnO/Ag₃PO₄ composite photocatalytic material, with excellent visible light catalytic performance, was prepared with the method of precipitation and deposition. Some characterization methods, includingXRD, XPS, SEM, EDS, BET, FTIR, UV-Vis DRS, PLand ESR were adopted to characterize and analyze the crystal structure, morphology, and optical properties of ZnO/Ag₃PO₄ composite photocatalytic material. Meanwhile, the photocatalytic degradation performance of GO-ZnO/Ag₃PO₄ with different ratios of graphene oxideto simulation antibiotics wastewater ciprofloxacin (CIP) was explored. The introduction of GO and ZnO enhances the visible light absorption of GO-ZnO/Ag₃PO₄, and makes GO-ZnO/Ag₃PO₄have better separation efficiency of electron-hole pairs. When the mass fraction of GO is 1wt%, GO-ZnO/Ag₃PO₄ displays the best photocatalytic activity, and the degradation rate of CIP can reach 85.3% after 60 minutes of visible light. The capture experimentprove that, in the reaction process, superoxide radical (·O₂^–) is the main active substance, and a heterojunction is formed between ZnO and Ag₃PO₄, which conforms to the Z-scheme electron transfer mechanism. The introduction of GO furtherly improves the rapid transfer of electrons and makes the Z-scheme system more stable. After six photocatalytic cycles, the degradation rate remained above 70%, indicating that the GO-ZnO/Ag₃PO₄ composite material has excellent stability.
- graphene /
- GO-ZnO/Ag₃PO₄ /
- photocatalysis /
- heterojunction /
- ciprofloxacin /
- composite

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图 1 纯ZnO、Ag₃PO₄、ZAP和GZAP-4的XRD图谱

Figure 1. XRD patterns of pure ZnO, Ag₃PO₄, ZAP and GZAP-4

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图 2 GZAP-4的XPS图谱：(a)全谱；(b) C 1s；(c) Ag 3d；(d) Zn 2p

Figure 2. XPS diagram of GZAP-4：(a) Full spectrum; (b) C 1s; (c) Ag 3d; (d) Zn 2p

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图 3 纯ZnO、Ag₃PO₄、ZAP和GZAP-4的FTIR图谱

Figure 3. FTIR images of pure ZnO, Ag₃PO₄, ZAP and GZAP-4

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图 4 样品的SEM图像

Figure 4. SEM image of the samples ((a) Pure ZnO; (b) Pure Ag₃PO₄; (c) ZAP; (d) GZAP-4)

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图 5 GZAP-4的EDS图谱

Figure 5. EDS diagram of GZAP-4

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图 6 Ag₃PO₄和GZAP-4的N₂吸附-解吸等温线

Figure 6. N₂ adsorption-desorption isotherm of Ag₃PO₄ and GZAP-4

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图 7 ZnO、Ag₃PO₄、ZAP和GZAP-4的UV-Vis DRS图(a)和Ag₃PO₄、ZAP和GZAP-4的PL光谱(b)

Figure 7. UV-Vis DRS diagram of ZnO, Ag₃PO₄, ZAP and GZAP-4 (a) as well as PL spectrum of Ag₃PO₄, ZAP and GZAP-4 (b)

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图 8 不同样品可见光降解CIP曲线(a)和对应样品准一级动力学拟合(b)

Figure 8. Visible light degradation curves of CIP by different samples (a) and quasi-first-order kinetic fitting of corresponding samples (b)

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图 9 GZAP-4循环6次光催化降解图

Figure 9. Photocatalytic degradation after 6 cycles of GZAP-4

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图 10 GZAP-4添加不同捕获剂对光催化的影响

Figure 10. The effect of adding different capture agents to GZAP-4 on photocatalysis

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图 11 可见光下Ag₃PO₄和GZAP-4的ESR DMPO-·O₂⁻光谱

Figure 11. ESR DMPO-·O₂⁻spectrum of Ag₃PO₄ and GZAP-4 under visible light

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图 12 ZnO和Ag₃PO₄的禁带宽度计算

Figure 12. Calculation of the band gap of ZnO and Ag₃PO₄

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图 13 GO-ZnO/Ag₃PO₄的光催化机制示意图

Figure 13. Schematic diagram of the photocatalytic mechanism of GO-ZnO/Ag₃PO₄

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表 1 复合材料命名

Table 1. Composite name

Composite name	Mass ratio of GO to Ag₃PO₄/%	Lable
ZnO/Ag₃PO₄	0	ZAP
1GO-Ag₃PO₄	1	GAP
0.1GO-ZnO/Ag₃PO₄	0.1	GZAP-1
0.2GO-ZnO/Ag₃PO₄	0.2	GZAP-2
0.5GO-ZnO/Ag₃PO₄	0.5	GZAP-3
1GO-ZnO/Ag₃PO₄	1	GZAP-4
2GO-ZnO/Ag₃PO₄	2	GZAP-5

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表 2 Ag₃PO₄和GZAP-4的比表面积、孔径及孔体积数据

Table 2. Specific surface area, pore size and pore volume data of Ag₃PO₄ and GZAP-4

Sample	Surface area/ (m²·g⁻¹)	Average pore sizes/nm	Pore volume/(cm³·g⁻¹)
Ag₃PO₄	9.59	8.51	0.0077
GZAP-4	16.47	6.23	0.0751

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