Design，preparation of benzimidazole-based porous polymers and its rapid adsorption of chlortetracycline

doi:10.19965/j.cnki.iwt.2022-0413

Abstract

Abstract:

The adsorption rate and efficiency of chlortetracycline by common adsorbents are very limited. In this work，benzimidazole as functional monomer，two benzimidazole-based hyper-crosslinked polymers，HCP-DCX and HCP-BCMBP，were synthesized by one-step Friedel-Crafts alkylation reaction using 1，4-benzyl dichloride（DCX） and 1，4-bibenzyl dichloride（BCMBP） as crosslinking agents，respectively. It was found that the crosslinking agent had an important effect on the morphology，composition and pore structure of polymers. HCP-BCMBP possessed a hierarchical pore structure formed by the random stacking of massive nanoparticles. The BET specific surface （1 397 m²/g），pore volume （1.488 cm³/g） and nitrogen content （0.96%） of HCP-BCMBP were significantly higher than those of HCP-DCX. As a result，HCP-BCMBP showed a better adsorption performance for chlortetracycline. Under the condition of pH=5，the initial mass concentration of chlortetracycline was 500 mg/L，and the mass concentration of HCP-BCMBP dosing was 1.0 g/L，the adsorption capacity of HCP-BCMBP could reach 413 mg/g within 30 min.It was obviously superior to that of other adsorbents reported. In addition，the adsorption kinetics，adsorption isotherm and adsorption mechanism of chlortetracycline on polymer were analyzed，and it was confirmed that hydrogen bond，π-π interaction and electrostatic interaction were the main adsorption mechanisms.

Key words: hyper-crosslinked, chlortetracycline, hierarchical pore, adsorption, dynamics

摘要：

普通吸附剂对金霉素吸附速率慢、效率低。以苯并咪唑为功能单体，1，4-二氯苄（DCX）和1，4-联苯二氯苄（BCMBP）分别为交联剂，通过一步Friedel-Crafts反应合成了超交联聚合物HCP-DCX和HCP-BCMBP。比较发现，交联剂对聚合物的形貌、组成、孔结构都产生了重要影响，HCP-BCMBP是由纳米颗粒随机堆积连接而成的多级孔结构，其BET比表面积（1 397 m²/g）、孔容（1.488 cm³/g）、含氮质量分数（0.96%）均显著高于HCP-DCX。因此，HCP-BCMBP对金霉素表现出更为优异的吸附性能，在pH=5，金霉素初始质量浓度为500 mg/L，HCP-BCMBP投加质量浓度为1.0 g/L条件下，30 min内HCP-BCMBP对金霉素的吸附量可达413 mg/g，与已报道的其他吸附剂相比有明显的优势。此外，分析了超交联聚合物吸附金霉素的动力学、吸附等温线及吸附机理，证实氢键、π-π作用、静电作用是主要的吸附机制。

关键词: 超交联, 金霉素, 分级孔, 吸附, 动力学

CLC Number:

TQ424

Lili ZHANG, Hai NAN, Huaxin ZHANG. Design，preparation of benzimidazole-based porous polymers and its rapid adsorption of chlortetracycline[J]. Industrial Water Treatment, 2023, 43(3): 64-70.

张丽丽, 南海, 张华新. 苯并咪唑基多孔聚合物的设计、制备及快速吸附金霉素研究[J]. 工业水处理, 2023, 43(3): 64-70.

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URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2022-0413

https://www.iwt.cn/EN/Y2023/V43/I3/64

Figures/Tables 9

References 16

1	GAO Chuanzi， HE Haihong， QIU Wenhui，et al. Oxidative stress，endocrine disturbance，and immune interference in humans showed relationships to serum bisphenol concentrations in a dense industrial area［J］. Environmental Science & Technology，2021，55（3）：1953-1963. doi:10.1021/acs.est.0c07587
2	霍荣帆，张瀚文，刘垒，等. 硝基芳香化合物废水处理技术研究进展［J/OL］. 工业水处理，DOI：10. 19965/j. cnki. iwt. 2022-0008 .
	HUO Rongfan， ZHANG Hanwen， LIU Lei，et al. Research progress on wastewater treatment technology of nitroaromatic compounds［J/OL］. Industrial Water Treatment，DOI：10. 19965/j. cnki. iwt. 2022-0008 .
3	SANTOS A D， VIANTE M F， POCHAPSKI D J，et al. Enhanced removal of p-nitrophenol from aqueous media by montmorillonite clay modified with a cationic surfactant［J］. Journal of Hazardous Materials，2018，355：136-144. doi:10.1016/j.jhazmat.2018.02.041
4	MIAO Jiahe， WANG Fenghe， CHEN Yajun，et al. The adsorption performance of tetracyclines on magnetic graphene oxide：A novel antibiotics absorbent［J］. Applied Surface Science，2019，475：549-558. doi:10.1016/j.apsusc.2019.01.036
5	ÁLVAREZ-TORRELLAS S， RODRÍGUEZ A， OVEJERO G，et al. Comparative adsorption performance of ibuprofen and tetracycline from aqueous solution by carbonaceous materials［J］. Chemical Engineering Journal，2016，283：936-947. doi:10.1016/j.cej.2015.08.023
6	谭良骁，谭必恩. 超交联微孔聚合物研究进展［J］. 化学学报，2015，73（6）：530-540. doi:10.6023/a15020096
	TAN Liangxiao， TAN Bien. Research progress in hypercrosslinked microporous organic polymers［J］. Acta Chimica Sinica，2015，73（6）：530-540. doi:10.6023/a15020096
7	WAHEED A， BAIG N， ULLAH N，et al. Removal of hazardous dyes，toxic metal ions and organic pollutants from wastewater by using porous hyper-cross-linked polymeric materials：A review of recent advances［J］. Journal of Environmental Management，2021，287：112360. doi:10.1016/j.jenvman.2021.112360
8	ZHANG Chun， ZHU Pengcheng， TAN Liangxiao，et al. Triptycene-based hyper-cross-linked polymer sponge for gas storage and water treatment［J］. Macromolecules，2015，48（23）：8509-8514. doi:10.1021/acs.macromol.5b02222
9	LUO Yali， LI Buyi， WANG Wei，et al. Hypercrosslinked aromatic heterocyclic microporous polymers：A new class of highly selective CO₂ capturing materials［J］. Advanced Materials，2012，24（42）：5703-5707. doi:10.1002/adma.201202447
10	CHEN Dongyang， GU Shuai， FU Yu，et al. Tunable porosity of nanoporous organic polymers with hierarchical pores for enhanced CO₂ capture［J］. Polymer Chemistry，2016，7（20）：3416-3422. doi:10.1039/c6py00278a
11	刘艳芳，高玮，尹思婕，等. 铁锆改性生物炭对水中磷吸附特性及机理研究［J］. 工业水处理，2022，42（11）：153-161.
	LIU Yanfang， GAO Wei， YIN Sijie，et al. Adsorption characteristics and mechanism of phosphorus in wastewater by iron-zirconium modified biochar［J］. Industrial Water Treatment，2022，42（11）：153-161.
12	LI Zhaoqian， QI Mengyu， TU Chunyan，et al. Highly efficient removal of chlorotetracycline from aqueous solution using graphene oxide/TiO₂ composite：Properties and mechanism［J］. Applied Surface Science，2017，425：765-775. doi:10.1016/j.apsusc.2017.07.027
13	LOU Yaoyin， YE Zhilong， CHEN Shaohua，et al. Sorption behavior of tetracyclines on suspended organic matters originating from swine wastewater［J］. Journal of Environmental Sciences，2018，65：144-152. doi:10.1016/j.jes.2017.03.019
14	FAN Hongtao， SHI Liqi， SHEN Hua，et al. Equilibrium，isotherm，kinetic and thermodynamic studies for removal of tetracycline antibiotics by adsorption onto hazelnut shell derived activated carbons from aqueous media［J］. RSC Advances，2016，6（111）：109983-109991. doi:10.1039/c6ra23346e
15	ZHANG Di， NIU Hongyun， ZHANG Xiaole，et al. Strong adsorption of chlorotetracycline on magnetite nanoparticles［J］. Journal of Hazardous Materials，2011，192（3）：1088-1093. doi:10.1016/j.jhazmat.2011.06.015
16	YANG Hongmei， ZHANG Lili， SHI Hong，et al. Hierarchical tetrazolium-based hyper-crosslinked polymer for rapid nitrophenol removal from wastewater［J］. Microporous and Mesoporous Materials，2022，337：111936. doi:10.1016/j.micromeso.2022.111936

吸附质	吸附剂	CTC初始质量浓度/（mg·L^-1）	温度/K	平衡时间/min	参考文献
CTC	氧化石墨烯/二氧化钛	100	308	1 200	〔12〕
	悬浮有机物	250	293	360	〔13〕
	榛子壳活性炭	1 000	293	20	〔14〕
	磁铁矿纳米颗粒	50	298	600	〔15〕
	磁性石墨烯氧化物	50	313	480	〔4〕
	HCP-BCMBP	500	298	30	本研究

吸附质	吸附剂	CTC初始质量浓度/（mg·L^-1）	温度/K	平衡时间/min	参考文献
CTC	氧化石墨烯/二氧化钛	100	308	1 200	〔12〕
	悬浮有机物	250	293	360	〔13〕
	榛子壳活性炭	1 000	293	20	〔14〕
	磁铁矿纳米颗粒	50	298	600	〔15〕
	磁性石墨烯氧化物	50	313	480	〔4〕
	HCP-BCMBP	500	298	30	本研究

吸附剂	Langmuir			Freundlich
吸附剂	Q_max/（mg·g^-1）	K_L/（L·mg^-1）	R²	K_F/ 〔（mg·g^-1）（L·mg^-1）^1/ⁿ 〕	1/n	R²
HCP-DCX	147	0.106	0.995	64.4	0.142	0.992
HCP-BCMBP	437	0.216	0.990	159	0.222	0.998

吸附剂	Langmuir			Freundlich
吸附剂	Q_max/（mg·g^-1）	K_L/（L·mg^-1）	R²	K_F/ 〔（mg·g^-1）（L·mg^-1）^1/ⁿ 〕	1/n	R²
HCP-DCX	147	0.106	0.995	64.4	0.142	0.992
HCP-BCMBP	437	0.216	0.990	159	0.222	0.998

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