温度敏感凝胶对铀的吸附性能及机理研究
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摘要
以经济、环境友好地方式从水中吸附铀具有重要的科学和现实意义。以壳聚糖（Chitosan，简称CS）为吸附功能组分，以N_-异丙基丙烯酰胺（N_-Isopropylacrylamide，简称NIPAAm）为温度响应组分，采用互穿网络技术（IPN）、大孔技术、离子印迹技术（IIT）等方法方法，制备对水中的铀具有温度转变控制吸附/解吸功能的温度敏感智能聚合物，实现对铀的绿色解吸，研究了其对铀吸附行为的影响。通过红外光谱分析（FT-IR），扫描电镜（SEM）形态分析等手段，结合吸附等温线拟合，吸附热力学试验和吸附动力学试验。
利用互穿网络技术将CS作为金属离子的接受体引入到温敏响应的聚N_-异丙基丙烯酰胺（PNIPAAm）水凝胶中，制备了温度敏感聚N_-异丙基丙烯酰胺/壳聚糖半互穿网络温敏水凝胶水凝胶（PNIPAAm/CS semi-IPN hydrogels）。测试了不同温度和pH值下semi-IPN水凝胶的溶胀性能。用制备的水凝胶研究了不同条件下对铀的吸附性能。动力学研究证明一级动力学模型比二级动力学模型更易拟合实验数据。为讨论在温度高于和低于最低临界共溶温度（LCST）半互穿网络水凝胶对铀的吸附机理，朗缪尔和弗伦德里希吸附模型被用于描述在293K和323K下的凝胶对铀的吸附等温线。在不同温度下的吸附结果表明PNIPAAm/CS水凝胶在低温下吸附UO22+离子。ΔH和ΔS的负值说明半互穿网络PNIPAAm/CS水凝胶对铀的吸附是自发放热的过程，并且温度升高自由能ΔG的值也升高说明吸附过程更易在低温下进行。
为了提高PNIPAAm/CS半互穿网络温敏水凝胶对铀的吸附作用，利用制孔的原理，制备了大孔PNIPAAm/CS semi-IPN凝胶。用扫描电镜和红外光谱法对凝胶进行了表征。研究了该水凝胶的溶胀性、温敏性。研究了在不同温度、时间下大孔凝胶对铀的吸附性能。将该大孔凝胶对铀溶液进行吸附，结果显示：PNIPAAm/CSsemi-IPN水凝胶对铀的吸附效果明显增大，在303K下，吸附时间为2h时达到吸附平衡，对铀的吸附量为115mg/g。同时，测定了温度变化对铀吸附的影响，结果表明，在LCST左右，有最大吸附量,当温度升高，该凝胶的吸附性能下降。
离子印迹在重金属离子的吸附研究中已经有了广泛的应用，印迹聚合物对模板离子有较高的吸附能力和较强的识别特性。因此，对PNIPAAm/CS凝胶进行了改进，制备了铀模板印迹的PNIPAAm/CS semi-IPN水凝胶。用制备的凝胶对铀离子进行了吸附试验。实验结果表明，凝胶对铀的吸附在6h达到平衡，最大吸附量为89mg/g。
Absorption of uranium from aqueous solutions with environmentically friendly andeconomic methods has great scientific value and realistic significance. Thermosensitivesmart gel, which could control the process of adsorption and desorption of uranium, wasprepared by introducing chitosan (CS) as adsorption component and N_-Isopropylacrylamide (NIPAAm) as thermosensitive component with IPN、porous techniques andion-imprinted techniques (IIT). The prepared gels were characterized by FTIR and SEManalysis. The kinetic, thermodynamic adsorption and adsorption isotherms of U(VI) ionswere studied in a batch adsorption experiments.
Thermo-sensitive semi-inter-penetrating network (semi-IPN) hydrogels were preparedby introducing CS as a metal ion receptor into the poly(N_-isopropylacrylamide)(PNIPAAm) hydrogels with an IPN technique. The swelling behavior of the semi-IPNhydrogels under different temperatures was studied. Feasibility of U(VI) sorption usingthe prepared hydrogels were investigated at different optimized conditions. The kineticstudy demonstrated that the pseudo-first-order model correlated with the experimentaldata better than the pseudo-second-order model examined. To discuss the mechanism ofadsorption of uranium(VI) ions on the semi-IPN hydrogels at temperature above andbelow the lower critical solution temperature (LCST), Langmuir and Freundlichadsorption models were applied to describe the isotherms at293and323K. Theadsorption results at different temperature showed that the PNIPAAm/CS hydrogelsadsorbed UO22+ions at lower temperature. Thermodynamic parameters such as enthalpychange (ΔH), entropy change (ΔS), free energy change (ΔG) were determined. Thenegative values of ΔH and ΔS indicated that the spontaneous nature and exothermicprocess of the U(VI) adsorption. The increase in the value of ΔG with a rise intemperature showed that the sorption was more favorable to low temperature.
Porous poly(N_-isopropylacrylamide)/chitosan IPN were prepared by suspendedemulsion polymerization to improve the adsorption ability of uranium. The porous IPN hydrogels were characterized by FTIR and SEM analysis. The swelling behavior,temperature sensitivity, pH sensitivity were investigated. The results indicated that theporous IPN hydrogels exhibited pH and temperature-sensitivity. And the uraniumadsorption onto porous PNIPAAm/CS increased obviously. At303K,2h, the maximunadsorption amount was115mg/g. The behavior of the porous hydrogels towardUranium(VI) at different temperatures were studied, the result showed that the uraniumadsorption amount decreased as temperature increased.And at LCST, the hydrogel hadmaximum adsorption amount.
Ion imprinted technology was applied widely in industrial analysis, ion imprintedpolymer has high adsorption capacity and selectivity. Therefore, uranium imprintedPNIPAAm/CS semi-IPN hydrogels were prepared by IIT．The adsorption capacity for theuranium(VI) ions of the hydrogels were systematically studied in this paper. The resultsshowed that the sorption equilibrium was achieved in6h and the maximum sorption ofuranium(VI) imprinted polymer was about89mg/g.
利用互穿网络技术将CS作为金属离子的接受体引入到温敏响应的聚N_-异丙基丙烯酰胺（PNIPAAm）水凝胶中，制备了温度敏感聚N_-异丙基丙烯酰胺/壳聚糖半互穿网络温敏水凝胶水凝胶（PNIPAAm/CS semi-IPN hydrogels）。测试了不同温度和pH值下semi-IPN水凝胶的溶胀性能。用制备的水凝胶研究了不同条件下对铀的吸附性能。动力学研究证明一级动力学模型比二级动力学模型更易拟合实验数据。为讨论在温度高于和低于最低临界共溶温度（LCST）半互穿网络水凝胶对铀的吸附机理，朗缪尔和弗伦德里希吸附模型被用于描述在293K和323K下的凝胶对铀的吸附等温线。在不同温度下的吸附结果表明PNIPAAm/CS水凝胶在低温下吸附UO22+离子。ΔH和ΔS的负值说明半互穿网络PNIPAAm/CS水凝胶对铀的吸附是自发放热的过程，并且温度升高自由能ΔG的值也升高说明吸附过程更易在低温下进行。
为了提高PNIPAAm/CS半互穿网络温敏水凝胶对铀的吸附作用，利用制孔的原理，制备了大孔PNIPAAm/CS semi-IPN凝胶。用扫描电镜和红外光谱法对凝胶进行了表征。研究了该水凝胶的溶胀性、温敏性。研究了在不同温度、时间下大孔凝胶对铀的吸附性能。将该大孔凝胶对铀溶液进行吸附，结果显示：PNIPAAm/CSsemi-IPN水凝胶对铀的吸附效果明显增大，在303K下，吸附时间为2h时达到吸附平衡，对铀的吸附量为115mg/g。同时，测定了温度变化对铀吸附的影响，结果表明，在LCST左右，有最大吸附量,当温度升高，该凝胶的吸附性能下降。
离子印迹在重金属离子的吸附研究中已经有了广泛的应用，印迹聚合物对模板离子有较高的吸附能力和较强的识别特性。因此，对PNIPAAm/CS凝胶进行了改进，制备了铀模板印迹的PNIPAAm/CS semi-IPN水凝胶。用制备的凝胶对铀离子进行了吸附试验。实验结果表明，凝胶对铀的吸附在6h达到平衡，最大吸附量为89mg/g。
Absorption of uranium from aqueous solutions with environmentically friendly andeconomic methods has great scientific value and realistic significance. Thermosensitivesmart gel, which could control the process of adsorption and desorption of uranium, wasprepared by introducing chitosan (CS) as adsorption component and N_-Isopropylacrylamide (NIPAAm) as thermosensitive component with IPN、porous techniques andion-imprinted techniques (IIT). The prepared gels were characterized by FTIR and SEManalysis. The kinetic, thermodynamic adsorption and adsorption isotherms of U(VI) ionswere studied in a batch adsorption experiments.
Thermo-sensitive semi-inter-penetrating network (semi-IPN) hydrogels were preparedby introducing CS as a metal ion receptor into the poly(N_-isopropylacrylamide)(PNIPAAm) hydrogels with an IPN technique. The swelling behavior of the semi-IPNhydrogels under different temperatures was studied. Feasibility of U(VI) sorption usingthe prepared hydrogels were investigated at different optimized conditions. The kineticstudy demonstrated that the pseudo-first-order model correlated with the experimentaldata better than the pseudo-second-order model examined. To discuss the mechanism ofadsorption of uranium(VI) ions on the semi-IPN hydrogels at temperature above andbelow the lower critical solution temperature (LCST), Langmuir and Freundlichadsorption models were applied to describe the isotherms at293and323K. Theadsorption results at different temperature showed that the PNIPAAm/CS hydrogelsadsorbed UO22+ions at lower temperature. Thermodynamic parameters such as enthalpychange (ΔH), entropy change (ΔS), free energy change (ΔG) were determined. Thenegative values of ΔH and ΔS indicated that the spontaneous nature and exothermicprocess of the U(VI) adsorption. The increase in the value of ΔG with a rise intemperature showed that the sorption was more favorable to low temperature.
Porous poly(N_-isopropylacrylamide)/chitosan IPN were prepared by suspendedemulsion polymerization to improve the adsorption ability of uranium. The porous IPN hydrogels were characterized by FTIR and SEM analysis. The swelling behavior,temperature sensitivity, pH sensitivity were investigated. The results indicated that theporous IPN hydrogels exhibited pH and temperature-sensitivity. And the uraniumadsorption onto porous PNIPAAm/CS increased obviously. At303K,2h, the maximunadsorption amount was115mg/g. The behavior of the porous hydrogels towardUranium(VI) at different temperatures were studied, the result showed that the uraniumadsorption amount decreased as temperature increased.And at LCST, the hydrogel hadmaximum adsorption amount.
Ion imprinted technology was applied widely in industrial analysis, ion imprintedpolymer has high adsorption capacity and selectivity. Therefore, uranium imprintedPNIPAAm/CS semi-IPN hydrogels were prepared by IIT．The adsorption capacity for theuranium(VI) ions of the hydrogels were systematically studied in this paper. The resultsshowed that the sorption equilibrium was achieved in6h and the maximum sorption ofuranium(VI) imprinted polymer was about89mg/g.
引文
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[1] J. Chen, H. Park, K. Park. Synthesis of superporous hydrogels: Hydrogels with fast swelling andsuperabsorbent properties. Journal of biomedical materials research,1999(44)53-62
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[1] J. Chen, H. Park, K. Park. Synthesis of superporous hydrogels: Hydrogels with fast swelling andsuperabsorbent properties. Journal of biomedical materials research,1999(44)53-62
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[8] W. Weber, J. Morris. Intraparticle diffusion during the sorption of surfactants onto activated carbon. JSanit Eng Div Am Soc Civ Eng,1963(89):53-61
[9] A. Kilislioglu, B. Bilgin. Thermodynamic and kinetic investigations of uranium adsorption on amberliteIR-118H resin. Applied radiation and isotopes,2003(58):155-160
[1] O. Hayden, F. L. Dickert. Selective microorganism detection with cell surface imprinted polymers.Advanced Materials,2001(13)1480-1483
[2] L. Schweitz, L. I. Andersson, S. Nilsson. Capillary electrochromatography with predeterminedselectivity obtained through molecular imprinting. Analytical Chemistry,1997(69):1179-1183
[3] J. D. Lei, T. W. Tan. Enantioselective separation of naproxen and investigation of affinitychromatography model using molecular imprinting. Biochemical engineering journal,2002(11):175-179
[4] E. Caro, R. Marce, P. Cormack, D. Sherrington, F. Borrull. Synthesis and application of anoxytetracycline imprinted polymer for the solid-phase extraction of tetracycline antibiotics. Analyticachimica acta,2005(552):81-86
[5] Y. Zhai, Y. Liu, X. Chang, X. Ruan, J. Liu. Metal ion-small molecule complex imprinted polymermembranes: Preparation and separation characteristics. Reactive and Functional polymers,2008(68):284-291
[6] H. Huo, H. Su, T. Tan. Adsorption of Ag+by a surface molecular-imprinted biosorbent. Chemicalengineering journal,2009(150):139-144