Full length articleRapid adsorption of Pb, Cu and Cd from aqueous solutions by β-cyclodextrin polymers
Graphical abstract
Introduction
The presence of toxic heavy metals has caused a serious global health challenge to human society [1], [2]. It becomes a major water pollution problem in many countries because of the indiscriminate discharge of untreated wastewater [3]. Long-time of drinking water contaminated by heavy metals such as lead (Pb), copper (Cu), and cadmium (Cd) would result in cardiovascular, pulmonary, immunological, neurological, and endocrine disorders and cancers [4]. Thus, removing heavy metals from aqueous solutions has drawn more and more attentions these years [5]. Many stringent standards are established to control heavy metal concentrations in discharged water. Such a strict circumstance offers a huge opportunity for water treatment technologies [6]. To solve the heavy metal pollutions, it is of great significance to develop robust and effective purification processes of wastewaters contaminated by heavy metals.
So far, a mass of water treatment technologies have been developed and utilized to remove heavy metals (HMs) from water including ion exchange (IE) [7], membrane filtration [8], [9], coagulation-flocculation-sedimentation (CFS) [10] and adsorption [11], [12]. Among them, CFS is widely used owing to its simplicity and low cost. However, this method will generate a large volume of sludge with low density, which required further dewatering and disposal [13]. Membrane technology possesses high efficiency and small footprint while it also faces some limitations like high energy requirement, concentrated disposal and difficulty in maintenance [14], [15]. The disadvantage of ion exchange (IE) is the interference of competing ions and regeneration [16]. Different from those methods mentioned above, adsorption is a safe method with high effectiveness and low cost [17], [18], [19]. This method can remove soluble and insoluble pollutants effectively without generation of hazardous by-products [20], [21], [22], [23], [24], [25]. To date, a wide variety of adsorbents with specific affinity to HMs have been developed and applied into water treatment [26], [27], [28], [29], [30], [31], [32], [33]. However, there were still some problems unresolved associated with their applications, one of the most serious problems was the low adsorption rate. Most of the adsorbents needed a long time to get equilibrium, which would result in a large waste of energies. Thus, it's highly important to develop adsorbents with high adsorption rate at present.
Among the HMs adsorbents, β-cyclodextrin (β-CD) is an inexpensive, sustainably produced macrocycle of glucose, Due to the possibility in removing HMs from water through adsorption method, β-CD has drawn much attention in the present study [34], [35]. When used as an adsorbent, β-CD can encapsulate pollutants in aqueous solution to form well-defined host-guest complexes [34]. However, the application of β-CD was limited by the disadvantages of low surface areas and poor removal performance compared to conventional adsorbents like activated carbons [36], [37]. Thus, improving the surface areas and removal performance of HMs for this kind of inexpensive adsorbent is highly important for the moment.
In this study, to increase surface areas of β-CD, we crosslinked β-CD with cross-linking agent contained rigid aromatic groups like tetrafluoroterephthalonitrile. The rigid structure of tetrafluoroterephthalonitrile linked with β-CD would generate a high-surface-area and porous polymer of β-CD. Thus the adsorption capacity and adsorption rate would be largely improved. Here, Pb, Cu and Cd were selected as the representive heavy metals for the serious global health challenge to human society. The as-synthesized β-CD polymer can rapidly capture a variety of HMs with higher adsorption capacity and adsorption rate than other adsorbents. The adsorption behavior of β-CD polymer for Pb, Cu and Cd was investigated in the way of adsorption kinetics, isotherm and thermodynamic. The effects of pH and multi-component adsorption were examined. The mechanism of HMs removal was studied by FT-IR and XPS analyses to reveal the active sites in adsorption process.
Section snippets
Materials
All reagents used in our investigation are analytical grade and were purchased from Shanghai Chemical Reagents Company and used without further purification. The stock solutions of Pb, Cu and Cd were prepared with deionized water using Pb(NO3)2, Cd(NO3)2·4H2O and Cd(NO3)2.4H2O. The desired pH values of the working solutions were controlled by 0.1 mol/L HNO3/NaOH solution.
Synthesis of β-CD polymer
The synthesis process of β-CD polymer was shown in Fig. S1 (see Supplementary material). Tetrahydrofuran/dimethylformamide
Characterization of β-CD polymer
Fig. 1 showed the TEM image of the as-synthesized β-CD polymer, which demonstrated the porous structure of β-CD polymers. Fig. 2a presented the FT-IR spectra of β-CD polymer, β-CD monomer and tetrafluoroterephthalonitrile. The FT-IR spectrum of tetrafluoroterephthalonitrile showed absorbance at 2235 cm−1, which was corresponding to the nitrile stretch of tetrafluoroterephthalonitrile, the absorbance at 1670 cm−1 and 1463 cm−1 were corresponding to CC aromatic stretches [34]. C-F stretches, which
Conclusions
In summary, mesoporous β-CD polymers crosslinked with rigid aromatic groups were prepared and used for HMs removal for the first time. The negative charge and large BET surface area made β-CD polymer a wonderful adsorbent for Pb, Cu and Cd. The adsorption process of Pb, Cu and Cd happened rapidly and got equilibrium in 5 min. The adsorption process of Pb, Cu and Cd took place on heterogeneous surfaces that varied with surface coverage. The maximum of adsorption capacities at 25 °C for Pb, Cu and
Acknowledgments
This work was supported by the National Key Scientific Program-Nanoscience and Nanotechnology (Grant No. 2011CB933700), the CASHIPS Director's Fund (Grant No. YZJJ201617), the National Natural Science Foundation of China (21177131, 61273066, 11205204, 21105001, 21077106, and 61104205).
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These two authors contribute the same to this paper.