IL/GO/88A的制备及其对四环素的光催化降解性能

陈鸿毅; 华涛; 李冬梅; 程建华; 杜克斯

doi:10.12030/j.cjee.202101127

华南理工大学环境与能源学院，广州 510006

华南理工大学华南协同创新研究院，东莞 523808

作者简介: 陈鸿毅(1994—)，男，硕士研究生。研究方向：水污染控制。E-mail：353569948@qq.com

通讯作者: 程建华(1976—)，男，教授。研究方向：水污染控制。E-mail：jhcheng@scut.edu.cn;

基金项目:

国家自然科学基金资助项目(21976060)；东莞市引进创新科研团队项目(2020607263005)

中图分类号: X522

Synthesis of IL/GO/88A and its photocatalytic degradation performance for tetracycline

School of Environment and Energy, South China University of Technology, Guangzhou 510006, China

South China Institutes Collaborative Innovation, South China University of Technology, Dongguan 523808, China

Corresponding author: CHENG Jianhua, jhcheng@scut.edu.cn ;

摘要: 使用离子液体(ILs)辅助生长新型光催化材料IL/GO/88A用于降解四环素(TC)，使用XRD、FTIR、SEM、N₂吸附-脱附、UV-vis、EIS等方法分别对催化材料进行了表征分析，考察了催化剂投加量、pH、TC浓度对TC降解的影响。该复合材料表现出高效的TC降解效率。在催化剂投加量为0.30 g·L⁻¹、pH为5.7、TC溶度为10 mg·L⁻¹的条件下，光照180 min后，IL/GO/88A对TC的去除率达到95.7%。催化剂在重复利用3次后仍能保持稳定的性能。此外，阐明了吸附-光催化协同机理，并推断·OH、h⁺是主要的活性物种。本研究结果对开发高效MOFs光催化复合材料并用于处理含四环素废水提供了新思路。

Abstract: A novel photocatalyst IL/GO/88A was prepared for tetracycline (TC) degradation using the ionic liquids (ILs) assisted growth method. And the composite was characterized by XRD, SEM, N₂ adsorption-desorption, UV-vis and EIS. The effects of the catalyst dosages, pH, and TC concentration on TC degradation were investigated. The composite material exhibited highly efficient TC degradation efficiency. Nearly 95.7% of TC could be removed after 180 min irradiation by the IL/GO/88A with dosage of 0.30 g·L⁻¹ under the condition of 10 mg·L⁻¹ TC and pH = 5.7. The catalyst maintained stable performance after 3 consecutive times recycle. In addition, the mechanism of adsorption-photocatalysis synergy was clarified, and ·OH⁻ and h⁺were determined to be the main active species. The results of this research provides a new idea for the development of efficient MOFs photocatalytic composite materials treating tetracycline-containing wastewater.

Key words:

光催化剂

TC浓度/(mg·L⁻¹)

投加量/(g·L⁻¹)

去除率/%

时间/min

来源

IL/GO/88A

0.30

95.7

180

本研究

0.30

88.8

180

M-MIL-101(Fe)/TiO₂

1.00

91.2

180

[33]

UiO-66@35WG

1.66

84.0

[34]

BiOI/MIL-125(Ti)

0.25

70.0

240

[35]

BiOI@UIO-66(NH₂)@g-C₃N₄

0.20

80.0

180

[36]

Fe-MIL-101

0.50

96.6

180

[37]

IL/GO/88A的制备及其对四环素的光催化降解性能

通讯作者: 程建华(1976—)，男，教授。研究方向：水污染控制。E-mail：jhcheng@scut.edu.cn;

作者简介: 陈鸿毅(1994—)，男，硕士研究生。研究方向：水污染控制。E-mail：353569948@qq.com
1. 华南理工大学环境与能源学院，广州 510006

2. 华南理工大学华南协同创新研究院，东莞 523808

收稿日期: 2021-01-21

录用日期: 2021-03-12

网络出版日期: 2021-06-25

基金项目:

国家自然科学基金资助项目(21976060)；东莞市引进创新科研团队项目(2020607263005)

关键词:

Synthesis of IL/GO/88A and its photocatalytic degradation performance for tetracycline

Corresponding author: CHENG Jianhua, jhcheng@scut.edu.cn ;

1. School of Environment and Energy, South China University of Technology, Guangzhou 510006, China

2. South China Institutes Collaborative Innovation, South China University of Technology, Dongguan 523808, China

Received Date: 2021-01-21

Accepted Date: 2021-03-12

Available Online: 2021-06-25

Keywords:

全文HTML

四环素(TC)是一种典型的抗生素，被广泛应用于人体治疗、畜牧业和水产养殖^[1]。由于不能被人类和动物完全降解，摄入的TC只能通过粪便和尿液进入环境，经常在地表水、地下水，甚至饮用水中被检测到^[2]。持续存在的TC会对生态环境和人体健康造成极大的危害。因此，去除水中的四环素显得尤为重要。不同于高级氧化法、生物处理法、膜过滤法和吸附法^[3-6]，光催化降解法以其高效、低能耗、绿色环保等优点，在污水处理中表现出良好的应用前景^[7]。

金属有机骨架(MOFs)在光催化领域展现出的优异性能而备受关注^[8-10]。MIL-88A(Fe)因其很强的可见光响应且安全无毒，被应用于光催化废水处理中^[11]。但是，MIL-88A(Fe)由于有机配体的存在导致光催化剂光生电子-空穴对快速复合^[12]，且其较低的比表面积影响了其对污染物的吸附效果^[13]，从而限制了其光催化活性。已有研究利用氧化石墨烯(GO)促进MOFs的光生电荷的转移和传输，改善了材料的光催化性能，并且增强MOFs的稳定性^[14]。但GO表面官能团有限^[15]，不能为MOFs晶体提供充足的生长位点，无法提供更多的吸附活性位点，这些都将阻碍其对水中污染物的高效吸附。离子液体(ILs)是一种具有良好稳定性、电导性、安全性的绿色溶剂^[16]，可以提升复合材料的分散性、导电性、吸附性能^[17-19]等。此外，可以通过调节阴离子和阳离子的组成或在常规ILs的基础上，引入特定的基团(氨基)来获得功能化的离子液体以提供丰富的官能团，例如被用于酸性气体吸收的含胺基离子液体[TETAH]⁺[Ac]^−[20]。据调研，目前尚未见[TETAH]⁺[Ac]⁻辅助生长IL/GO/MOFs用于光催化降解水中四环素的报道。

在本研究中，采用[TETAH]⁺[Ac]⁻辅助生长手段制备了IL/GO/88A，详细考察了其表面形态、晶体结构以及电子和光学性能，充分评估了IL/GO/88A对TC的光催化降解的性能；同时，提出了吸附-光催化协同机理以解释TC可能的降解路径，以期为新型MOFs光催化复合材料的开发及其在水污染控制领域的应用提供参考。

1. 材料与方法

1.1. 实验原料

三亚乙基四胺(TETA, C₆H₁₈N₄)、冰乙酸(HAc, CH₃COOH)、六水合三氯化铁(FeCl₃·6H₂O)、反丁烯二酸(C₄H₄O₄)、四环素(C₂₂H₂₄N₂O₈)、异丙醇((CH₃)₂CHOH)、对苯醌(C₆H₄O₂)、乙醚(C₄H₁₀O)、乙醇(C₂H₅OH)、甲醇(CH₃OH)、氢氧化钠(NaOH)、盐酸(HCl)均为分析级纯，氧化石墨烯(GO)为实验室自制，实验用水为去离子水。

1.2. 催化剂的制备

用恒压漏斗将0.2 mol·L⁻¹ TETA溶液添加到等摩尔浓度的HAc溶液中，并在<15 ℃条件下搅拌6 h，所得溶液用乙醚萃取，在80 ℃下真空浓缩，直至达到无水状态，得到离子液体[TETAH]⁺[Ac]⁻。

将MOFs前驱体1.5 mmol FeCl₃·6H₂O和1.5 mmol C₄H₄O₄，投加到7.5 mL乙醇水溶液(V_乙醇∶V_水 = 1∶2)中，直到固体完全溶解。然后，将混合物转移到25 mL聚四氟乙烯内衬，密封在不锈钢高压釜中，并在65 ℃下加热12 h。待自然冷却后，分别用去离子水和无水乙醇洗涤纯化24 h。最后，将样品过滤并在50 ℃真空干燥12 h，收集橘红色粉末MIL-88A(Fe)^[21]。

将5.9 mg GO、1.5 mmol [TETAH]⁺[Ac]⁻和相同摩尔质量的MOFs前驱体投加到乙醇水溶液，重复上述MIL-88A(Fe)的制备步骤，得到棕色粉末IL/GO/88A。作为对照，制备未添加ILs的复合材料，标记为GO/88A。

1.3. 材料的表征仪器

本研究中，光催化剂表征所采用的仪器包括X射线衍射仪(Bruker D8 Advance，德国布鲁克公司)、傅里叶变换红外光谱(NICOLET 5700，美国尼高力仪器公司)、扫描电子显微镜(Merlin，德国卡尔·蔡司公司)、全自动比表面及孔隙度分析仪(ASAP 2460，美国麦克公司)、紫外可见分光光度计(UV-3600，日本岛津公司)、电化学工作站(CHI 760D，上海辰华仪器有限公司)。

1.4. TC的降解实验

实验装置以300 W Xe灯(λ > 420 nm)为实验光源，250 mL夹套烧杯为反应器。实验过程中，开启循环冷却水使装置温度稳定在(25 ± 2) ℃，将催化剂投加到装有200 mL TC溶液的反应器中，用0.1 mol·L⁻¹氢氧化钠和盐酸溶液调节反应溶液的pH，在黑暗条件下通过磁力搅拌60 min使催化剂达到吸附-解吸平衡，然后开启Xe灯照射悬浮液180 min，每个照射间隔采样2.0 mL并通过0.22 μm过滤器，使用紫外可见分光光度计(U-2910，日本日立公司)分析滤液中TC浓度，检测波长为357 nm。TC的去除率公式见式(1)。

式中：η为TC去除率；C₀为TC的初始浓度，mg·L⁻¹，C_t为t时刻对应的TC浓度, mg·L⁻¹。

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