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环境科学

一种评价光催化剂降解环境修复中抗生素性能的完整方法

Published: October 06, 2022
doi:
10.3791/64478
, , , , , , ,
1School of Chemical Engineering,Northwest University

Summary

这里介绍的是一个协议，以酞菁敏化磷酸银复合材料光催化去除水中抗生素有机污染物分子为例，探索一套通用的实验程序，用于环境净化领域的光催化剂的综合实验室评估。

Abstract

在地下水和土壤系统中大量发现各种抗生素，如四环素、金霉素、阿莫西林和左氧氟沙星，可能导致耐药和多重耐药细菌的发展，对人类、动物和环境系统构成威胁。光催化技术因其快速稳定的处理和直接利用太阳能而引起了人们的浓厚兴趣。然而，大多数评估半导体催化剂光催化降解水中有机污染物性能的研究目前尚未完成。本文设计了一个完整的实验方案，用于综合评价半导体催化剂的光催化性能。本文采用室温和常压下采用简单的溶剂相合成法制备菱形十二面体磷酸银。采用溶剂热法制备了Br次酞菁/Ag3PO4异质结材料。以300 W氙灯为模拟太阳光源，光强度为350 mW/cm 2，通过研究催化剂用量、温度、pH值、阴离子等不同影响因素，评价了制备的降解四环素材料的催化性能2。与第一个循环相比，构建的BrSubphthalocyanine/Ag 3PO 4在5次光催化循环后保持了82.0%的原始光催化活性，而原始Ag3PO4仅保持了28.6%。通过五循环实验进一步测试了磷酸银样品的稳定性。本文为实验室中评估半导体催化剂的催化性能提供了完整的流程，以开发具有实际应用潜力的半导体催化剂。

Introduction

四环素类（TCs）是常见的抗生素，可有效防止细菌感染，广泛用于畜牧业、水产养殖和疾病预防1，2。由于过去几十年的过度使用和不当应用，以及工业废水的排放，它们广泛分布在水中3.这造成了严重的环境污染和对人类健康的严重威胁;例如，水环境中TCs的过量存在会对微生物群落分布和细菌抗性产生负面影响，导致生态失衡，这主要是由于抗生素的高度亲水和生物蓄积性，以及一定程度的生物活性和稳定性4，5，6.由于TC在环境中的超稳定性，很难自然分解;因此，已经开发了许多方法，包括生物，物理化学和化学处理7，8，9。生物处理效率高，成本低10，11.然而，由于它们对微生物有毒，它们不能有效地降解和矿化水中的抗生素分子12。虽然物理化学方法可以直接快速地从废水中去除抗生素，但这种方法仅将抗生素分子从液相转化为固相，不能完全降解它们，并且成本太高13。

与传统方法相比，半导体光催化由于其高效的催化降解特性，在过去几十年中已被广泛用于污染物的降解14。例如，Li等人的无贵金属磁性FexMny催化剂在不使用任何氧化剂15的情况下实现了水中多种抗生素分子的高效光催化氧化。Yan等报道了在废弃生物质衍生碳上原位合成百合类NiCo2O4纳米片，以实现对水中酚类污染物的高效光催化去除16。该技术依靠由光激发的半导体催化剂来产生光生电子（e–）和空穴（h+）17。光生e–和h+通过与吸收的O 2和H 2 O反应转化为超氧阴离子自由基（O 2–）或羟基自由基（OH–），这些氧化活性物质氧化并将水中的有机污染物分子分解为CO 2和H 2 O以及其他较小的有机分子18，19，20.然而，光触媒性能评价尚无统一的现场标准。材料的光催化性能评价应从催化剂制备工艺、最佳催化性能的环境条件、催化剂回收性能等方面进行研究。Ag3PO4以其突出的光催化能力，在环境修复中引起了极大的关注。这种新型光催化剂在大于420nm的波长下可实现高达90%的量子效率，明显高于先前报道的值21。然而，Ag3PO4的严重光腐蚀和不理想的电子空穴分离率限制了其广泛的应用22。因此，已经进行了各种尝试来克服这些缺点，例如形状优化23，离子掺杂24和异质结构构建25，26，27。本文采用形貌控制和异质结工程对Ag3PO4进行了修饰。首先，在室温常压下通过溶剂相合成制备了具有高表面能的菱形十二面体Ag3PO4晶体。然后，采用溶剂热法将兼具电子受体和电子供体的有机超分子BrSubphthalocyanine（BrSubPc）自组装在磷酸银表面28，29，30，31，32，33，34，35.通过研究不同环境因素对制备样品降解水中痕量四环素的光催化性能的影响，评价了所制备材料的光催化性能。本文为材料的光催化性能的系统评价提供了参考，对未来光催化材料在环境修复中的实际应用具有重要意义。

Protocol

1. 准备 BrSubPc 注意：BrSubPc 样品是根据先前发表的工作36 制备的。反应在双排管真空管路系统中进行，反应过程在无水和无氧条件下严格控制。 原料预处理称取2克邻二氰基苯，在真空烘箱中干燥24小时，取出，然后在玛瑙研钵中小心研磨。 再次放入真空烤箱中1周;然后，将其取出并放入干燥器中。 测量50mL邻二氯苯?…

Representative Results

采用该溶剂相合成法成功合成了菱形十二面体Ag3PO4。图1A，B所示的SEM图像证实了这一点。根据SEM分析，发现菱形十二面体结构的平均直径在2-3μm之间。原始的BrSubPc微晶显示出大的不规则薄片结构（图1C）。在复合样品中，二氧化钛仍保持了原来的纳米球结构，但没有发现酞菁片结构，这意味着酞菁分子均匀地自组装在钛白?…

Discussion

在本文中，我们提出了一种评估光催化材料催化性能的完整方法，包括催化剂的制备、影响光催化的因素的研究以及催化剂回收性能。该评价方法是通用的，适用于所有光催化材料性能评价。

在材料制备方法方面，已经报道了许多使用不同前体21，22制备菱形十二面体Ag3PO4的方案。我们采用的方法在Ag3PO4…

Disclosures

The authors have nothing to disclose.

Acknowledgements

这项工作得到了国家自然科学基金（21606180）和陕西省自然科学基础研究计划（计划编号：2019JM-589）的支持。

Materials

300 W xenon lamp CeauLight CEL-HXF300
AgNO3 Aladdin Reagent (Shanghai) Co., Ltd. 7783-99-5
Air Pump Samson Group Co. ACO-001
BBr3 Bailingwei Technology Co., Ltd. 10294-33-4
Constant temperature circulating water bath Beijing Changliu Scientific Instruments Co. HX-105
Dichloromethane Tianjin Kemiou Chemical Reagent Co., Ltd. 75-09-2
Ethanol Tianjin Fuyu Fine Chemical Co., Ltd. 64-17-5
Fourier-transform infrared Bruker Vector002
Hexane Tianjin Kemiou Chemical Reagent Co., Ltd. 110-54-3
HNO3 Aladdin Reagent (Shanghai) Co., Ltd. 7697-37-2
ICP-OES Aglient 5110
K2HPO4 Aladdin Reagent (Shanghai) Co., Ltd. 16788-57-1
Magnesium Sulfate Tianjin Kemiou Chemical Reagent Co., Ltd. 10034-99-8
Methanol Tianjin Kemiou Chemical Reagent Co., Ltd. 67-56-1
NaOH Aladdin Reagent (Shanghai) Co., Ltd. 1310-73-2
NH4NO3 Sinopharm Group Chemical Reagent Co., Ltd. 6484-52-2
o-dichlorobenzene Tianjin Fuyu Fine Chemical Co., Ltd. 95-50-1
o-dicyanobenzene Sinopharm Group Chemical Reagent Co., Ltd. 91-15-6
Scanning electron microscopy JEOL JSM-6390
Trichloromethane Tianjin Kemiou Chemical Reagent Co., Ltd. 67-66-3
Ultraviolet-visible Spectrophotometer Shimadzu UV-3600
X-ray diffractometer Rigaku D/max-IIIA
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Tags

Keywords: Photocatalyst Performance EvaluationSemiconductor CatalystsEnvironmental RemediationAmmonium NitrateSilver PhosphateBromine SubphthalocyanineCatalyst SynthesisCatalyst Characterization
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Wang, B., Zhang, X., Li, L., Ji, M., Zheng, Z., Shi, C., Li, Z., Hao, H. A Complete Method for Evaluating the Performance of Photocatalysts for the Degradation of Antibiotics in Environmental Remediation. J. Vis. Exp. (188), e64478, doi:10.3791/64478 (2022).
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