基于PVC基体的铵离子敏感膜制备及性能表征  

Preparation and performance characterization of ammonium ion sensitive bembrane based on PVC substrate

作　　者：雒建中 柏源 韦飞 周香 刘田田 梅蓉 金奇杰 徐海涛 闫新龙[5] 林正根 LUO Jianzhong;BAI Yuan;ZHOU Xiang;LIU Tiantian;MEI Rong;JIN Qijie;XU Haitao;YAN Xinlong;LIN Zhenggen(China Energy Investment Corporation,Beijing 100011,China;Guodian Environmental Protection Research Institute Co.,Ltd.,Nanjing 210031,Jiangsu China;China Energy Science and Technology Research Institute Co.,Ltd.,Nanjing 210023,Jiangsu China;School of Environmental Science and Engineering,Nanjing Tech University,Nanjing 211816,Jiangsu China;School of Chemical Engineering and Technology,China University of Mining and Technology,Xuzhou 221116,Jiangsu China)

机构地区：[1]国家能源投资集团有限责任公司,北京100011 [2]国电环境保护研究院有限公司,江苏南京210031 [3]国家能源集团科学技术研究院有限公司,江苏南京210023 [4]南京工业大学环境科学与工程学院,江苏南京211816 [5]中国矿业大学化工学院,江苏徐州221116

出　　处：《电力科技与环保》2024年第4期416-426,共11页Electric Power Technology and Environmental Protection

基　　金：国家自然科学基金项目(22378417);国家能源集团科学技术研究院有限公司科技项目(HB2023Y02)。

摘　　要：铵离子选择电极是电厂脱硫废水氨氮检测传感器的核心部件,而铵离子敏感膜是影响传感器电极性能的关键因素。为获得性能较好的铵离子敏感膜,本文以PVC为敏感膜基体,针对增塑剂、离子添加剂和离子载体的这3种添加剂的组合变化筛选最佳配方组合,并表征和分析其对电极响应性能的影响,以及敏感膜性能参数的变化规律,同时考察了Li^(+)、Na^(+)等9类干扰离子对电极选择性及抗干扰能力的影响。结果表明:敏感膜的最佳配方为50%邻苯二甲酸二丁酯+0.75%四(4-氯苯基)硼酸钾+1.20%无活菌素,基底PVC与邻苯二甲酸二丁酯的质量比为1:1,与溶剂四氢呋喃的质量比为1:20。该配方下敏感膜的探测下限为1.26×10^(-5)mol/L;当氯化铵溶液浓度大于0.001 mol/L时,响应时间为0.5~2.0s;浓度小于0.001 mol/L时,响应时间则延长至约5 s;重现性测试显示,相对标准偏差均小于2%;电极寿命超过90 d,性能良好。多种表征结果显示膜具有无定形的微观结构,各组分良好的相容性有利于强化NH+4的响应稳定性。加入增塑剂和离子添加剂后,离子载体的主要结构未发生明显改变,膜的完整性能够保持;9类离子选择性系数均小于0,干扰性均较小。其中K^(+)干扰最大,可以通过K+浓度修正方程解决,从而提高氨氮检测的准确性。Ammonium ion selective electrode is an important component of ammonia nitrogen water detection sensor,and ammonium ion sensitive membrane is a key factor affecting electrode performance.Effects of plasticizers,ion additives,and ion carriers on response performance of ammonium ion selective electrodes were investigated,and the changes in performance parameters of the prepared electrode sensitive membrane were also explored,in which PVC was used as sensitive membrane substrate.The effects of 9 types of interfering ions such as Li^(+)and Na^(+)on electrode selectivity and anti-interference ability were also studied in this paper.The research results indicate that the optimal formula for the sensitive membrane is 50%DBP+0.75%KTPClPB+1.20%non bacterial agent.Mass ratio of the substrate PVC to DBP is 1:1,and mass ratio to solvent(PVC:THF)is about 1:20.The lower detection limit of the sensitive film under this formula is 1.26×10^(-5)mol/L.When the concentration of ammonium chloride solution is greater than 10^(-3)mol/L,the response time is 0.5-2.0 s.While its concentration is less than 10^(-3)mol/L,the response time is extended to about 5s;The relative standard deviation of the reproducibility performance test is less than 2%,and the electrode life exceeds 90 days,indicating good performance.The characterization results such as XRD show that the membrane has an amorphous microstructure,and the good compatibility of each component is beneficial for enhancing the NH^(4+)response stability.After adding plasticizers and ionic additives,significant changes about main structure of the ion carrier are not appeared,which indicating integrity of the membrane.Selectivity coefficients of all 9 types of ions are less than 0,indicating that the interference is relatively small.Among them,K+interference is the largest,which can be solved by the proposed K+concentration correction equation,thereby improving the accuracy of ammonia nitrogen ion detection.

关 键 词：脱硫废水 铵离子选择电极 敏感膜 增塑剂 电极性能 

分 类 号：TK417[动力工程及工程热物理—动力机械及工程] X773[环境科学与工程—环境工程]