聚吡咯纳米线凝胶的模板制备及储能与电化学传感性能

doi:10.7503/cjcu20190266

摘要/Abstract

摘要：

以配位聚合物凝胶为模板, 构筑均一的聚吡咯纳米线网络, 聚合后经简单处理除去模板, 得到性能优异的聚吡咯凝胶. 结果表明, 模板法合成的聚吡咯凝胶为由均一纳米线组成的三维网络结构, 具有良好的力学性能、较大的比表面积及优异的电化学特性, 在0.28 A/g电流密度下, 比电容可达450 F/g, 在2.8 A/g电流密度下充放电1000次, 比电容仍可保持88.6%. 聚吡咯纳米线网络凝胶经葡萄糖氧化酶负载后得到柔性传感电极, 对低浓度(0.2 mmol/L)的葡萄糖具有快速响应性能, 有望用于超级电容器及生物电化学传感器等领域.

关键词: 聚吡咯纳米线, 凝胶, 模板合成, 超级电容器, 电化学传感器

Abstract:

Conducting polymer gels possess both gel-network structure and organic semiconductor properties, thus exhibit high energy density, excellent charge-discharge stability, and good flexibility, etc. They are considered as ideal materials for producing flexible electrodes, however the traditional fabrication of conducting polymer gels often introduced non-conducting chemical crosslinkers, limiting the electrical conductivity. In this work, a coordination polymer gel was employed as template to produce uniform network of polypyrrole nanowires, and after polymerization the template could be easily removed thereby improving the performance of the polypyrrole gel. The results showed that the polypyrrole gel fabricated by template method had a three-dimensional network structure composed of uniform nanowires, having good mechanical properties, large specific surface area, and excellent electrochemical properties. At a current density of 0.28 A/g, the specific capacitance could reach 450 F/g, meanwhile the the specific capacitance could be maintained at 88.6% after 1000 times charge-discharge cycles at a current density of 2.8 A/g. The polypyrrole nanowire network gels were loaded with glucose oxidase to give a flexible sensor, which had rapid responsiveness to glucose at low concentration(0.2 mmol/L), therefore they were expected to have application in supercapacitors, electrochemical sensors and so on.

Key words: Polypyrrole nanowires, Gel, Templating fabrication, Supercapacitor, Electrochemical sensor

中图分类号:

O631

李勃天,邵伟,肖达,周雪,董俊伟,唐黎明. 聚吡咯纳米线凝胶的模板制备及储能与电化学传感性能[J]. 高等学校化学学报, 2020, 41(1): 183-190.

LI Botian,SHAO Wei,XIAO Da,ZHOU Xue,DONG Junwei,TANG Liming. Polypyrrole Nanowire Gels Based on Templating Fabrication and Their Energy Storage and Electrochemical Sensing Properties ^†[J]. Chemical Journal of Chinese Universities, 2020, 41(1): 183-190.

图/表 9

Scheme 1 Synthesis route of polypyrrole nanowire gel based on templating fabrication(A) and molecular structure of ligand L(B)

Fig.1 SEM images of Ag-L(A), APS-PPy(B) and FN-PPy(C)

Fig.2 Storage modulus(G', a, c, e) and loss modulus(G″, b, d, f) of APS-PPy(a, b), FN-PPy(c, d) and Ag-L(e, f) at different frequency(strain=0.1%, A) and at different strain(f=1 Hz, B)

Fig.3 N2 adsorption(a)/desorption(b) isotherms(A, C) and pore size distributions(B, D) of APS-PPy(A, B) and FN-PPy(C, D)

Fig.4 Impedance curve(A), the cyclic voltammogram curves at different scan rates(B), the galvanostatic discharge profiles at various current densities(C) and the summary plot of specific capacitance values vs. current density(D) of APS-PPy gel electrode supercapacitor (B) Scan rate/(mV·s-1): a. 5; b. 10; c. 20; d. 50; e. 100. (C) Current rate/(A·g-1): a. 0.24; b. 0.48; c. 0.96; d. 2.4; e. 4.8. Inset in (D): cycling test showing ca. 72% capacitance retention over 1000 cycles at high current rate of 4.8 A/g.

Fig.5 Impedance curve(A), the cyclic voltammogram curves at different scan rates(B), the galvanostatic discharge profiles at various current densities(C) and the summary plot of specific capacitance values vs. current density(D) of FN-PPy gel electrode supercapacitor (B) Scan rate/(mV·s-1): a. 5; b. 10; c. 20; d. 50; e. 100. (C) Current density/(A·g-1): a. 0.28; b. 0.72; c. 1.44; d. 2.17; e. 2.8. Inset in (D): cycling test showing ca. 89% capacitance retention over 1000 cycles at high current rate of 4.8 A/g.

Fig.6 N1s(A) and Fe2p(B) XPS spectra of FN-PPy gel (A) a. C—N(Fe)—C; b. C—N+—C; c. C—NH—C. (B) a. Fe2p1/23+; b. Fe2p1/22+; c. Fe2p3/23+; d. Fe2p3/22+.

Fig.7 APS-PPy gel network structured electrode for biosensor showing amperometric response to increasing concentration(0.2 mmol/L for each time) of glucose(A) and the corresponding plot of amperometric response vs. glucose concentration(B) Inset of (A) shows a magnification of the seventh additions of glucose.

Fig.8 FN-PPy gel network structured electrode for biosensor showing amperometric response to increasing concentration(0.2 mmol/L for each time) of glucose(A) and the corresponding plot of amperometric response vs. glucose concentration(B) Inset of (A) shows a magnification of the sixth additions of glucose.

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