Facile Synthesis of Porous Organic Polymer/Chitosan Composites and the Removal Effect of Hg(Ⅱ)
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摘要:
特定多孔结构和杂原子掺杂的吸附剂对提高重金属离子的吸附性能具有重要意义。传统的多孔有机聚合物材料大多在溶剂中合成，且为粉末状的形式，但在合成方法优化和实际应用便捷性方面仍有一定的发展空间。本文针对水体中的汞污染，采用简单快速的机械研磨法以1,3,5-三醛基间苯三酚(Tp)和硫脲(TU)制备硫掺杂的多孔有机聚合物(TpTU)与壳聚糖(CS)复合材料TpTU@CS。采用X射线衍射光谱、N2吸附-解吸和傅里叶变换红外光谱等技术对TpTU@CS复合材料进行表征。通过扫描电镜证实了TpTU@CS复合材料的多孔结构。由于在分子网络中引入了−C=S−基团，合成的TpTU@CS在水溶液中对Hg(Ⅱ)具有更高的吸附选择性和亲和力，吸附容量高(249.21mg/g)，吸附动力学快(10min)。通过表征分析得出，TpTU@CS捕获Hg(Ⅱ)的主要机制是C=S中S与Hg的键合以及C−N与Hg(Ⅱ)的配位相互作用。与其他研究相比，TpTU@CS具有优异的吸附性能，且具有易于处理和可回收利用的优点。同时，该复合材料TpTU@CS对于Hg(Ⅱ)低浓度污染的实际水样和高浓度的加标水样，均具有较高的去除能力，去除率可达到77.0%～100.0%。
Abstract:Specific porous structures and heteroatom-doped adsorbents have great importance in improving the adsorption performance of heavy metal ions. Traditional porous organic polymer materials are mostly synthesized in solvents in the form of powder, so it is significant to develop a highly efficient adsorption material and apply it to the adsorption and removal of Hg(Ⅱ). In the research, S-doped porous organic polymer (TpTU) and chitosan (CS) composites TpTU@CS were prepared by using 1,3,5-trialaldehyde phloroglucinol (Tp) and thiourea (TU) by a simple and rapid mechanical grinding method. The TpTU@CS composites were characterized by X-ray diffraction spectroscopy, N2 adsorption-desorption, scanning electron microscope and Fourier transform infrared spectroscopy. Due to the introduction of the −C=S− group into the molecular network, the synthesized TpTU@CS has high adsorption selectivity and affinity for Hg(Ⅱ) in aqueous solution, with high adsorption capacity (249.21mg/g) and fast adsorption kinetics (10min). Through the characterization analysis, it is concluded that the main mechanism of trapping Hg(Ⅱ) by TpTU@CS is the bonding between S and Hg in C=S and the coordination interaction between C−N and Hg(Ⅱ). Meanwhile, the composite TpTU@CS has a high removal capacity (77.0%−100.0%) of Hg(Ⅱ) for both the actual samples and the marked samples. The BRIEF REPORT is available for this paper at
http://www.ykcs.ac.cn/en/article/doi/10.15898/j.ykcs.202211170219 . -
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表 1 TpTU@CS对Hg(Ⅱ)的吸附等温线和动力学拟合结果(25℃)
Table 1. Adsorption isotherms and kinetic fitting results of TpTU@CS adsorption on Hg(Ⅱ) at 25℃
吸附等温线 Freundlich吸附模型 Langmuir吸附模型 n KF (mg/g) R2 Qm (mg/g) KL (L/mg) R2 3.704 249.21 0.9659 227.52 0.79 0.9033 吸附动力学 拟一级动力学模型 拟二级动力学模型 k1 (min−1) Qe (mg/g) R2 k2 [g/(mg·min)] Qe (mg/g) R2 0.39 189.72 0.9938 0.003 202.53 0.9868 
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表 2 TpTU@CS处理实际水样中Hg(Ⅱ)的吸附效果
Table 2. Adsorption effect of Hg(Ⅱ) in real water samples pretreated by TpTU@CS
实际水样 Hg(Ⅱ)浓度
(μg/L)Hg(Ⅱ)去除率
(%)Hg(Ⅱ)加标浓度
(1mg/L)Hg(Ⅱ)加标浓度
(2mg/L)Hg(Ⅱ)加标浓度
(5mg/L)去除率
(%)RSD
(n=3)去除率
(%)RSD
(n=3)去除率
(%)RSD
(n=3)溪水 0.64 100.0 83.4 0.51 83.7 1.56 78.7 1.19 湖水 6.61 100.0 77.4 0.83 81.5 1.18 77.0 1.33 池塘水 9.72 100.0 78.6 1.19 79.8 1.29 78.9 0.62
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表 3 不同吸附剂对Hg(Ⅱ)去除效果的比较
Table 3. Comparison of removal effects of Hg(Ⅱ) pretreated with different adsorbents
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