Journal of Textile Research ›› 2023, Vol. 44 ›› Issue (08): 158-166.doi: 10.13475/j.fzxb.20220706501

• Dyeing and Finishing & Chemicals • Previous Articles     Next Articles

Preparation of β-cyclodextrin-based organic framework materials and their adsorption on heavy metal ions

WANG Chenyang, JIA Jie, LI Faxue()   

  1. College of Textiles, Donghua University, Shanghai 201620, China
  • Received:2022-07-14 Revised:2023-05-25 Online:2023-08-15 Published:2023-09-21

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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

CLC Number: 

  • TS193

Fig. 1

SEM images of β-CDMOF beforeand after cross-linking with different proportions of CA"

Fig. 2

FT-IR spectra of β-CDMOF and β-CDMOF/CA"

Fig. 3

XRD patterns of β-CDMOF and β-CDMOF/CA"

Tab. 1

Water solubility of β-CDMOF and β-CDMOF/CA"

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

Fig. 4

Changes of removal rate of Sb(Ⅲ)(a) and Pb(Ⅱ)(b) by β-CDMOF/CA versus pH values of ion solutions"

Fig. 5

Adsorption kinetic curves of Sb(Ⅲ) and Pb(Ⅱ) on β-CDMOF/CA. (a) Pseudo-first-order adsorption kinetic curve on Sb(Ⅲ); (b) Pseudo-second-order adsorption kinetic equation on Sb(Ⅲ); (c) Pseudo-first-order adsorption kinetic curve Pb(Ⅱ); (d) Pseudo-second-order adsorption kinetic curve Pb(Ⅱ)"

Tab. 2

Adsorption kinetic parameters of β-CDMOF/CA for Sb(Ⅲ) and Pb(Ⅱ)"

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
Qe/(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

Fig. 6

Adsorption isotherms of β-CDMOF/CA Sb(Ⅱ) and Pb(Ⅱ). (a) Langmuir adsorption isotherm model of β-CDMOF/CA on Sb(Ⅲ); (b) Freundlich adsorption isotherm model of β-CDMOF/CA on Sb(Ⅲ); (c) Langmuir adsorptionisotherm model of β-CDMOF/CA on Pb(Ⅱ); (d) Freundlich adsorption isoltherm model of β-CDMOF/CA on Pb(Ⅱ)"

Tab. 3

Isothermal adsorption parameters of β-CDMOF/CA for metal ions for Sb(Ⅲ) and Pb(Ⅱ)"

吸附剂种类 金属
离子		 实验吸
附量
Qe/
(mg·g-1)		 饱和吸
附量
qm/
(mg·g-1)		 R2
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

Fig. 7

Cyclic adsorption of β-CDMOF/CA to Sb(Ⅲ) and Pb(Ⅱ)"

Fig. 8

Zeta potential of β-CDMOF/CA versus pH value"

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