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一种具有高电催化活性的新型聚(3,4-亚乙基二氧噻吩)/铁酞菁/多壁碳纳米管纳米复合材料,用于亚硝酸盐氧化。

A novel poly(3,4-ethylenedioxythiophene)/iron phthalocyanine/multi-wall carbon nanotubes nanocomposite with high electrocatalytic activity for nitrite oxidation.

机构信息

Department of Chemical Engineering, National Taiwan University, Taipei 10617, Taiwan.

出版信息

Talanta. 2010 Oct 15;82(5):1905-11. doi: 10.1016/j.talanta.2010.08.010. Epub 2010 Aug 17.

Abstract

In the present work, the oxidative electrochemistry of nitrite on the poly(3,4-ethylenedioxythiophene)/iron phthalocyanine/multi-wall carbon nanotubes-(PEDOT/FePc/MWCNT) modified screen-printed carbon electrodes (SPCE) has been investigated. The parameters, such as overpotential, current density and rate constant at PEDOT/FePc/MWCNT-modified SPCE, were compared with an un-modified, FePc-, and FePc/MWCNT-modified SPCE for electro-oxidation of nitrite. As compared with the un-modified SPCE, an increase in the anodic peak current density (J(pa)) (∼100%) along with a decrease in the anodic peak potential (E(pa)) of ∼150mV for electro-oxidation of nitrite at the FePc-modified SPCE was observed. When an under-layer of MWCNT was introduced onto FePc-modified SPCE, denoted as FePc/MWCNT-modified SPCE, and the number of FePc/MWCNT bilayer was optimized, the heterogeneous electron transfer rate constant (k) at FePc/MWCNT-modified SPCE was enhanced about 7.8 times as compared with that at FePc-modified SPCE. Moreover, as a layer of PEDOT film was electrodeposited onto the FePc/MWCNT-modified SPCE, denoted as PEDOT/FePc/MWCNT-modified SPCE, a significant increase in current response along with a remarkable decrease in E(pa) were noticed. This can be attributed to the pre-concentration effect induced by the electrostatic interaction between the negatively charged nitrite and oxidized PEDOT film. On the whole, the PEDOT/FePc/MWCNT-modified SPCE greatly reduces the overpotential of ∼330mV along with 3.5 times enhanced the peak current density for the electro-oxidation of nitrite as compared with un-modified SPCE. The sensitivity and limit of detection (S/N=3) for the PEDOT/FePc/MWCNT-modified SPCE were found to be as 638mAcm(-2)M(-1) and 71nM, respectively. Notably, PEDOT/FePc/MWCNT-modified SPCE has a lower sensing potential than compared to several other modified electrodes. The developed sensor was also applied for the determination of nitrite in tap water sample.

摘要

在本工作中,研究了聚(3,4-亚乙基二氧噻吩)/铁酞菁/多壁碳纳米管-(PEDOT/FePc/MWCNT)修饰丝网印刷碳电极(SPCE)上的亚硝酸盐的氧化电化学。将修饰后的 SPCE 与未修饰的、FePc 修饰的和 FePc/MWCNT 修饰的 SPCE 相比,对亚硝酸盐在 PEDOT/FePc/MWCNT 修饰的 SPCE 上的电氧化的过电势、电流密度和速率常数等参数进行了比较。与未修饰的 SPCE 相比,在 FePc 修饰的 SPCE 上电氧化亚硝酸盐时,阳极峰电流密度(J(pa))增加了约 100%,阳极峰电位(E(pa))降低了约 150mV。当将 MWCNT 作为底层引入到 FePc 修饰的 SPCE 上,记为 FePc/MWCNT 修饰的 SPCE,并且优化了 FePc/MWCNT 双层的数量时,与 FePc 修饰的 SPCE 相比,FePc/MWCNT 修饰的 SPCE 的非均相电子转移速率常数(k)提高了约 7.8 倍。此外,当将一层 PEDOT 膜电沉积到 FePc/MWCNT 修饰的 SPCE 上,记为 PEDOT/FePc/MWCNT 修饰的 SPCE 时,发现电流响应显著增加,E(pa)明显降低。这可以归因于带负电荷的亚硝酸盐与氧化的 PEDOT 膜之间的静电相互作用引起的预浓缩效应。总的来说,与未修饰的 SPCE 相比,PEDOT/FePc/MWCNT 修饰的 SPCE 大大降低了约 330mV 的过电势,同时使亚硝酸盐电氧化的峰值电流密度提高了 3.5 倍。对于 PEDOT/FePc/MWCNT 修饰的 SPCE,灵敏度和检测限(S/N=3)分别为 638mAcm(-2)M(-1)和 71nM。值得注意的是,与其他一些修饰电极相比,PEDOT/FePc/MWCNT 修饰的 SPCE 的传感电位更低。所开发的传感器还用于测定自来水中的亚硝酸盐。

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