Electrochemical sensor for detecting both oxidizing and reducing compounds based on poly(ethyleneimine)/phosphotungstic acid multilayer film modified electrode

Abstract A novel electrochemical sensor was prepared by alternatively deposition of anionic phosphotungstic acid (PTA) and polyelectrolyte poly(ethyleneimine) (PEI) on ITO glass through Layer-by-Layer assembly technique. Ascorbic acid and H 2 O 2 were used as model drugs to investigate the electrocatalytic behavior of PEI/PTA multilayer film modified electrode in 0.1 M NaAc-HAc buffer (pH 5.0), respectively. The results showed that the corresponding current response of redox peak increased linearly with the increase of the concentration of them in certain ranges. The results of the standard addition method at three concentration levels testified that as-prepared electrode can be used to determine both of oxidizing and reducing compounds with low detection limits and high recoveries. And more, the response current of the electrode still can remain 96% of its initial activity after 100 cycles of CV scan. The PEI/PTA multilayer film modified electrode was further used to determine ascorbic acid in three commercially available fruit drinks, and the results were validated by high performance liquid chromatography, it was found that no statistically significant difference existed between the two methods. Compared with previous reports, the PEI/PTA multilayer film modified electrode can be used to determine both of oxidizing and reducing compounds with high sensitivity, good stability and reusability.

[1]  Guanggang Gao,et al.  Electrochromic ultra-thin films based on cerium polyoxometalate , 2004 .

[2]  E. Steckhan,et al.  Electrochemical Properties of Polyoxometalates as Electrocatalysts. , 1998, Chemical reviews.

[3]  E. Wang,et al.  Photochromic inorganic-organic multilayer films based on polyoxometalates and poly(ethylenimine). , 2004, Journal of colloid and interface science.

[4]  Wei Xing,et al.  Highly conductive, methanol resistant fuel cell membranes fabricated by layer-by-layer self-assembly of inorganic heteropolyacid , 2009 .

[5]  Freek Kapteijn,et al.  Highly dispersed platinum in metal organic framework NH2-MIL-101(Al) containing phosphotungstic acid – Characterization and catalytic performance , 2012 .

[6]  M. Kooti,et al.  Phosphotungstic acid supported on magnetic nanoparticles as an efficient reusable catalyst for epoxidation of alkenes , 2012 .

[7]  J. Cox,et al.  Preparation and electrocatalytic applications of a multilayer nanocomposite consisting of phosphomolybdate and poly(amidoamine) , 2001 .

[8]  J. Yao,et al.  Facile synthesis of a Ag nanoparticle/polyoxometalate/carbon nanotube tri-component hybrid and its activity in the electrocatalysis of oxygen reduction , 2011 .

[9]  Liya Zhang,et al.  Layer-by-layer assembly of chitosan/tungstosilicate acid-Ag nanocomplex with electrocatalytic properties , 2009 .

[10]  Shuang Li,et al.  A sensor of a polyoxometalate and Au–Pd alloy for simultaneously detection of dopamine and ascorbic acid , 2013 .

[11]  A. Gopalan,et al.  Electro-assisted fabrication of layer-by-layer assembled poly(2,5-dimethoxyaniline)/phosphotungstic acid modified electrode and electrocatalytic oxidation of ascorbic acid , 2008 .

[12]  E. Coronado,et al.  Application of the Langmuir–Blodgett Technique to Polyoxometalates: Towards New Magnetic Films , 1997 .

[13]  Changwen Hu,et al.  Photoluminescent organic–inorganic composite films layer-by-layer self-assembled from the rare-earth-containing polyoxometalate Na9[EuW10O36] and poly(allylamine hydrochloride) , 2002 .

[14]  Yu-Fei Song,et al.  Recent advances on polyoxometalate-based molecular and composite materials. , 2012, Chemical Society reviews.

[15]  J. Schlenoff,et al.  Sprayed Polyelectrolyte Multilayers , 2000 .

[16]  H. Trang.  Development of HPLC methods for the determination of water-soluble vitamins in pharmaceuticals and fortified food products , 2013 .

[17]  F. Yin,et al.  Studies on the electrocatalytic oxidation of dopamine at phosphotungstic acid–ZnO spun fiber-modified electrode , 2013 .

[18]  Zhongbo Hu,et al.  Study of the ferrocenylalkanethiol self-assembled monolayers by electrochemical surface plasmon resonance , 2007 .

[19]  Zu-liang Chen,et al.  In situ electro-deposition of Pt micro-nano clusters on the surface of {[PMo12O40]3-/PAMAM}n multilayer composite films and their electrocatalytic activities regarding methanol oxidation. , 2012, Journal of colloid and interface science.

[20]  Hui Zhang,et al.  Layer-by-layer inkjet printing of fabricating reduced graphene-polyoxometalate composite film for chemical sensors. , 2012, Physical chemistry chemical physics : PCCP.

[21]  S. Dong,et al.  Assembly of multilayer films containing iron(III)-substituted Dawson-type heteropolyanions and its electrocatalytic properties: cyclic voltammetry, electrochemical impedance spectroscopy and UV-Vis spectrometry , 2003 .

[22]  E. Wang,et al.  Inorganic-organic hybrid polyoxometalate containing supramolecular helical chains : Preparation, characterization and application in chemically bulk-modified electrode , 2005 .

[23]  A. Gopalan,et al.  Layer-by-layer electrochemical assembly of poly(diphenylamine)/phosphotungstic acid as ascorbic acid sensor , 2009 .

[24]  D. Ingersoll,et al.  Polyoxometallate‐Based Layered Composite Films on Electrodes Preparation Through Alternate Immersions in Modification Solutions , 1994 .

[25]  P. Kulesza,et al.  Voltammetry of phosphotungstic acid immobilized in templated silica gel , 1998 .

[26]  P. Gómez‐Romero,et al.  Polyoxometalates: from inorganic chemistry to materials science. , 2004, Frontiers in bioscience : a journal and virtual library.

[27]  J. Hao,et al.  Fabrication and electrocatalytic activities of porphyrin and 12-molybdophosphoric acid hybrid films. , 2010, Journal of colloid and interface science.

[28]  R. Thouvenot,et al.  Functionalization of polyoxometalates: towards advanced applications in catalysis and materials science. , 2008, Chemical communications.

[29]  Vijay Ramani,et al.  Investigation of Nafion ® /HPA composite membranes for high temperature/low relative humidity PEMFC operation , 2004 .

[30]  P. Kulesza,et al.  Phosphomolybdate-modified multi-walled carbon nanotubes as effective mediating systems for electrocatalytic reduction of bromate. , 2009, Analytica chimica acta.