基于碳纳米管/Ag/MoS_2转导层的全固态钙离子选择电极
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摘要
构建了一种电势稳定性好的全固态钙离子选择电极(Ca~(2+)-ISE),采用碳纳米管(CNT)/Ag/MoS_2为转导层,自制的三脚架化合物作为钙离子载体,制备固体接触式Ca~(2+)-ISE。系统分析了全固态Ca~(2+)-ISE的稳定性、能斯特斜率、响应范围、选择性系数等主要性能,发现制备的固体接触式Ca~(2+)-ISE在钙离子浓度为1×10~(-6)～1×10~(-1)mol/L范围内呈现线性能斯特响应,响应斜率为28. 1 mV/decade。CNT/Ag/MoS_2的引入有利于提高固体接触式Ca~(2+)-ISE的离子浓度线性响应范围,缩短电势平衡时间,降低测试能斯特斜率与理论值差,对于Ca~(2+)-ISE的长期在线检测有重要研究意义。
An all-solid-state Ca~(2+) ion selective electrode( Ca~(2+)-ISE) was prepared with carbon nanotube( CNT)/Ag/MoS_2 as the ion-to-electron transducer and tripodal compound as the calcium ionophore. The stability,slope,response range,selectivity coefficient,etc. of the electrode were investigated. It is revealed that the electrode exhibits a 28. 1 mV/decade Nernst slope in the range of 1 × 10~(-6)～ 1 × 10~(-1) mol/L Ca~(2+) concentration. The transducer is helpful in enlarging the linear response range of the Ca~(2+)concentration,shortening the potential balance time and reducing the difference of the Nernst slope. All of these results are important for long-term online detection of calcium ions for the solid electrode.
An all-solid-state Ca~(2+) ion selective electrode( Ca~(2+)-ISE) was prepared with carbon nanotube( CNT)/Ag/MoS_2 as the ion-to-electron transducer and tripodal compound as the calcium ionophore. The stability,slope,response range,selectivity coefficient,etc. of the electrode were investigated. It is revealed that the electrode exhibits a 28. 1 mV/decade Nernst slope in the range of 1 × 10~(-6)～ 1 × 10~(-1) mol/L Ca~(2+) concentration. The transducer is helpful in enlarging the linear response range of the Ca~(2+)concentration,shortening the potential balance time and reducing the difference of the Nernst slope. All of these results are important for long-term online detection of calcium ions for the solid electrode.
引文
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[22]LU Huijie,GAO Qiaoying,YAN Zhenning,et al. Calcium Ion Selective Electrode with 1,1,1-tris(N-Methyl-Nphenylaminocarbonylmethoxymethyl)Propane as Ionophore[J]. J Instrum Anal,2003,22(1):9-11(in Chinese).卢慧杰,高巧英,颜振宁,等.以1,1,1,-三(N-甲基-N-苯基氨基羰甲氧基)丙烷为载体的钙离子选择电极[J].分析测试学报,2003,22(1):9-11.
[2]WU Nengyou,ZHANG Bidong,WU Daidai. The Mechanism of Marine Calcium Isotope Fractionation and Its Paleoceanographic Application[J]. Adv Earth Sci,2015,30(4):433-444(in Chinese).吴能友,张必东,邬黛黛.海洋钙同位素分馏机制及其古海洋学应用[J].地球科学进展,2015,30(4):433-444.
[3]WEI Lingyun,JI Jun,HU Guoyuan. The Importance of Calcium to Life Growth and Its Nutritional Function[J]. Trace Elem Health Stud,2010,27(5):60-62(in Chinese).魏凌云,戢峻,胡国元.钙对生命成长的重要性及其营养功能[J].微量元素与健康研究,2010,27(5):60-62.
[4]LI Xingui,YU Wenhui,HUANG Meirong. Progress and Applications of Calcium Ion-Selective Electrode[J]. Chem Sens,2016,36(4):15-24(in Chinese).李新贵,蔚文慧,黄美荣.钙离子选择电极的发展现状及应用[J].化学传感器,2016,36(4):15-24.
[5]ZENG Xianzhong. The Construction of Solid Ion Selective Electrode Detection System and Its Application in Potassium and Calcium Analysis of Seawater[D]. Beijing:University Chinese Academy Science,2017(in Chinese).曾现忠.固态离子选择性电极检测体系的构建及其在海水钾、钙分析中的应用[D].北京:中国科学院大学,2017
[6]Bobacka J. Potential Stability of All-Solid-State Ion-Selective Electrodes Using Conducting Polymers as Ion-to-Electron Transducers[J]. Anal Chem,1999,71:4932-4937.
[7]Li X G,Feng H,Huang M R,et al. Ultrasensitive Pb(Ⅱ)Potentiometric Sensor Based on Copolyaniline Nanoparticles in a Plasticizer-Free Membrane with a Long Lifetime[J]. Anal Chem,2011,84(1):134-140.
[8]Huang M R,Ding Y B,Li X G,et al. Synthesis of Semiconducting Polymer Microparticles as Solid Ionophore with Abundant Complexing Sites for Long-Life Pb(Ⅱ)Sensors[J]. ACS Appl Mater Interfaces,2014,6(24):22096-22107.
[9]Huang M R,Rao X W,Li X G,et al. Lead Ion-Selective Electrodes Based on Polyphenylenediamine as Unique Solid Ionophores[J]. Talanta,2011,85(3):1575-1584.
[10]Huang M R,Ding Y B,Li X G. Lead-Ion Potentiometric Sensor Based on Electrically Conducting Microparticles of Sulfonic Phenylenediamine Copolymer[J]. Analyst,2013,138(13):3820-3829.
[11]Bobacka J. Conducting Polymer-Based Solid-State Ion-Selective Electrodes[J]. Electroanalysis,2006,18:7-18.
[12]Cattrall R W,Drew D M,Hamilton I C. Some Alkylphosphoric Acid-Esters for Use in Coated-Wire Calcium-Selective Electrodes. 1. Response Characteristics[J]. Anal Chim Acta,1975,76:269-277.
[13]Cattrall R W,Newlands M J,Mackay M F. Some Alkylphosphoric Acid-Esters for Use in Coated-Wire Calcium-Selective Electrodes[J]. Anal Chim Acta,1983,155:235-242.
[14]Yin T J,Qin W. Applications of Nanomaterials in Potentiometric Sensors[J]. Trends Anal Chem,2013,51:79-86.
[15]Hu J B,Stein A,B ehlmann P. Rational Design of All-Solid-State Ion-Selective Electrodes and Reference Electrodes[J].Trends Anal Chem,2016,76:102-114.
[16]Bakker E,Pretsch E. Modern Potentiometry[J]. Angew Chem Int Ed,2007,46:5660-5668.
[17]Zhou M,Gan S,Cai B,et al. Effective Solid Contact for Ion-Selective Electrodes:Tetraks(4-chlorophenyl)borate Anions Doped Nanocluster Films[J]. Anal Chem,2012,84:3480-3483.
[18]Zou X U,Cheong J H,Taitt B J,et al. Solid Contact Ion-Selective Electrodes with a Well-Controlled Co(Ⅱ)/Co(Ⅲ)Redox Buffer Layer[J]. Anal Chem,2013,85:9350-9355.
[19]Veder J P,De-Marco R,Patel K,et al. Evidence for a Surface Confined Ion-to-Electron Transduction Reaction in SolidContact Ion-Selective Electrodes Based on Poly(3-octylthiophene)[J]. Anal Chem,2013,85:10495-10502.
[20] Crespo G A,Macho S,Xavier F. Ion-Selective Electrodes Using Carbon Nanotubes as Ion-to-Electron Transducers[J].Anal Chem,2008,80:1316-1322.
[21]LU Huijie,YI Mingcai,FAN Yaoting. Development of Tripod Structure Ccompounds and Complexes[J]. J Inorg Chem,2001,17(4):478-488(in Chinese).卢会杰,尹明彩,樊耀亭.三脚架结构化合物及配合物研究进展[J].无机化学学报,2001,17(4):478-488.
[22]LU Huijie,GAO Qiaoying,YAN Zhenning,et al. Calcium Ion Selective Electrode with 1,1,1-tris(N-Methyl-Nphenylaminocarbonylmethoxymethyl)Propane as Ionophore[J]. J Instrum Anal,2003,22(1):9-11(in Chinese).卢慧杰,高巧英,颜振宁,等.以1,1,1,-三(N-甲基-N-苯基氨基羰甲氧基)丙烷为载体的钙离子选择电极[J].分析测试学报,2003,22(1):9-11.
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