β-环糊精基金属有机框架材料的制备及其对重金属离子的吸附

doi:10.13475/j.fzxb.20220706501

摘要/Abstract

摘要：

为获得成本较低、绿色环保和优良吸附特性的重金属吸附材料,采用水热法合成了β-环糊精(β-CD)基金属有机骨架材料(β-CDMOF);利用柠檬酸(CA)作为交联剂,制备了一系列具有良好水稳定性的β-CD基吸附剂(β-CDMOF/CA)。并以印染废水中主要的重金属离子Sb(Ⅲ)、Pb(Ⅱ)为吸附对象,探讨了吸附剂对2种重金属离子的吸附性能。结果表明,当CA用量为β-CDMOF质量的3倍时,所制备的吸附剂 β-CDMOF/CA(1∶3)对2种金属离子的吸附容量最高,吸附过程符合Langmuir吸附等温模型,均遵循准二级动力学方程,即化学吸附;当Sb(Ⅲ)、 Pb(Ⅱ)溶液pH值分别为6和5时,β-CDMOF/CA(1∶3)对它们的饱和吸附量分别达到515.46和591.71 mg/g; 经过5 次吸附-解吸附后, β-CDMOF/CA(1∶3)对Sb(Ⅲ)、Pb(Ⅱ)的去除率仍高于75%,具有稳定的循环吸附性能。

关键词: β-环糊精基金属有机骨架材料, 印染废水, 重金属离子, 吸附

Abstract:

Objective Heavy metal ions as a common toxic substance in printing and dyeing wastewater cause great harm and much efforts have been made to treat the wastewater aiming to reducing the concentration of heavy metal ions. The adsorption method has the advantages of simple operation, high efficiency and no secondary pollution. As a novel adsorbent, β-cyclodextrin organic skeleton material is explored for adsorbability for heavy metal ions along with simple, eco-friendly and low-cost preparation.

Method β-cyclodextrin organic matrix (β-CDMOF) was synthesized by hydrothermal method with β-cyclodextrin and potassium chloride as raw materials. A series of β-cyclodextrin based adsorbents (β-CDMOF/CA) with good water stability were prepared by using citric acid as crosslinking agent and controlling the different feeding ratios of β-cyclodextrin based MOFs and citric acid in the reaction process, and were named as β-CDMOF/CA (1∶1), β-CDMOF/CA (1∶2) and β-CDMOF/CA (1∶3), respectively. The structures of these adsorbents were analyzed by SEM, FT-IR and XRD, and the adsorption properties of these adsorbents for Sb(Ⅲ) and Pb(Ⅱ) ions were studied.

Results Compared with the irregular morphology of β-CDMOF, the crosslinked β-CDMOF/CA exhibited more regular appearance, and more stable appearance with the increase of CA addition, indicating significant improvement with crosslinking treatment in morphological stability of the prepared adsorbent (Fig. 1). The main frame and structural integrity of β-CD were preserved during the cross-linking process of CA (Fig. 2). The cross-linking reaction between CA and β-CDMOF resulted in the continuous reduction in the crystallinity and the gradual change of crystal structure of β-CDMOF (Fig. 3). The water stability of the adsorbent was gradually enhanced with the increase of crosslinking. The adsorption process of the prepared three adsorbents for Sb(Ⅲ) and Pb(Ⅱ) accorded with the Langmuir adsorption isothermal model and the quasi second-order adsorption kinetic equation, namely chemical adsorption. β-CDMOF/CA(1∶3) demonstrated the best adsorption performance, and its maximum saturated adsorption capacity to Sb(Ⅲ) and Pb(Ⅱ) reached 515.46 and 591.71 mg/g, respectively. After 5 times of adsorption-desorption, the removal rate of Sb(Ⅲ) and Pb(Ⅱ) by β-CDMOF/CA(1∶3) was still higher than 75%, showing a stable cyclic adsorption performance. The adsorption mechanism of Sb(Ⅲ) and Pb(Ⅱ) by the adsorbent was mainly determined through electrostatic interaction and chelation.

Conclusion β-CDMOF was synthesized by hydrothermal method with β-CD and KCl as raw materials, and then the adsorbent β-CDMOF/CA with good water stability and heavy metal ion adsorption was prepared by crosslinking with CA. The results show that the prepared adsorbent is a crystal with relatively uniform size, and its solubility in water is lower than 0.034 g/L, which is easy to filter and separate from wastewater. The adsorption results show that the maximum adsorption capacities of β-CDMOF/CA for Sb(Ⅲ) and Pb(Ⅱ) are 515.46 mg/g and 591.71 mg/g, respectively. The adsorption kinetic results show that the adsorption process of β-CDMOF/CA for two metal ions conforms to the pseudo-second-order kinetic model, which is a chemical adsorption process. After 5 times of adsorption-desorption cycles, the removal rate of β-CDMOF/CA for two metal ions is still more than 75%, indicating good recycling performance. The adsorbent developed in this research has the characteristics of low cost, simple preparation, green environmental protection and excellent adsorption performance, and shows a good application prospect for the treatment of heavy metal ions in textile printing and dyeing wastewater.

Key words: β-Cyclodextrin-based metal-organic frameworks, printing and dyeing wastewater, heavy metal ions, adsorption

中图分类号:

TS193

王宸杨, 贾洁, 李发学. β-环糊精基金属有机框架材料的制备及其对重金属离子的吸附[J]. 纺织学报, 2023, 44(08): 158-166.

WANG Chenyang, JIA Jie, LI Faxue. Preparation of β-cyclodextrin-based organic framework materials and their adsorption on heavy metal ions[J]. Journal of Textile Research, 2023, 44(08): 158-166.

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参考文献 20

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样品	初始质量 m₀/g	未溶解部分质量m/g	溶剂体积 V/L	溶解度S/ (g·L^-1)
β-CDMOF	0.05	0.000 4	0.25	0.198
β-CDMOF/CA(1∶1)	0.05	0.041 4	0.25	0.034
β-CDMOF/CA(1∶2)	0.05	0.042 3	0.25	0.031
β-CDMOF/CA(1∶3)	0.05	0.043 8	0.25	0.025

吸附剂种类	金属离子	一级动力学R²	二级动力学R²	平衡吸附量 Q_e/(mg·g^-1)
β-CDMOF/CA(1:1)	Sb(Ⅲ)⁺	0.991	0.999	62.35
β-CDMOF/CA(1:2)		0.996	0.999	56.57
β-CDMOF/CA(1:3)		0.975	0.999	64.00
β-CDMOF/CA(1:1)	Pb(Ⅱ)	0.845	0.999	79.95
β-CDMOF/CA(1:2)		0.983	0.999	83.89
β-CDMOF/CA(1:3)		0.935	1	85.63

吸附剂种类	金属离子	实验吸附量 Q_e/ (mg·g^-1)	饱和吸附量 q_m/ (mg·g^-1)	R²
吸附剂种类	金属离子	实验吸附量 Q_e/ (mg·g^-1)	饱和吸附量 q_m/ (mg·g^-1)	Lang- muir 模型	Freun- dlich 模型
β-CDMOF/CA(1∶1)	Sb(Ⅲ)	480.70	483.09	0.964	0.952
β-CDMOF/CA(1∶2)		375.09	370.37	0.950	0.920
β-CDMOF/CA(1∶3)		513.19	515.46	0.990	0.981
β-CDMOF/CA(1∶1)	Pb(Ⅱ)	445.54	462.96	0.993	0.990
β-CDMOF/CA(1∶2)		521.00	543.48	0.991	0.980
β-CDMOF/CA(1∶3)		551.28	591.71	0.987	0.968