Cobalt Phthalocyanine Modified Electrodes Utilised in Electroanalysis: Nano-Structured Modified Electrodes vs. Bulk Modified Screen-Printed Electrodes

Cobalt phthalocyanine (CoPC) compounds have been reported to provide electrocatalytic performances towards a substantial number of analytes. In these configurations, electrodes are typically constructed via drop casting the CoPC onto a supporting electrode substrate, while in other cases the CoPC complex is incorporated within the ink of a screen-printed sensor, providing a one-shot economical and disposable electrode configuration. In this paper we critically compare CoPC modified electrodes prepared by drop casting CoPC nanoparticles (nano-CoPC) onto a range of carbon based electrode substrates with that of CoPC bulk modified screen-printed electrodes in the sensing of the model analytes l-ascorbic acid, oxygen and hydrazine. It is found that no “electrocatalysis” is observed towards l-ascorbic acid using either of these CoPC modified electrode configurations and that the bare underlying carbon electrode is the origin of the obtained voltammetric signal, which gives rise to useful electroanalytical signatures, providing new insights into literature reports where “electrocatalysis” has been reported with no clear control experiments undertaken. On the other hand true electrocatalysis is observed towards hydrazine, where no such voltammetric features are witnessed on the bare underlying electrode substrate.

[1]  Tebello Nyokong,et al.  Comparison of carbon screen-printed and disk electrodes in the detection of antioxidants using CoPc derivatives , 2012 .

[2]  Jonathan P. Metters,et al.  Ultraflexible Screen‐Printed Graphitic Electroanalytical Sensing Platforms , 2014 .

[3]  Zhaoxia Wang,et al.  Electrochemical detection of dopamine in the presence of epinephrine, uric acid and ascorbic acid using a graphene-modified electrode , 2012 .

[4]  E. Gileadi,et al.  Defining the transfer coefficient in electrochemistry: An assessment (IUPAC Technical Report) , 2014 .

[5]  Dan Xiao,et al.  Electrochemical Detection of Dopamine in the Presence of Ascorbic Acid Using Overoxidized Polypyrrole/Graphene Modified Electrodes , 2011, International Journal of Electrochemical Science.

[6]  I. Kruusenberg,et al.  Oxygen electroreduction on multi-walled carbon nanotube supported metal phthalocyanines and porphyrins in alkaline media. , 2013, Journal of nanoscience and nanotechnology.

[7]  Kristopher R. Ward,et al.  Nanoparticle modified electrodes can show an apparent increase in electrode kinetics due solely to altered surface geometry: The effective electrochemical rate constant for non-flat and non-uniform electrode surfaces , 2013 .

[8]  R. Baldwin,et al.  Liquid chromatography/electrochemical detection of carbohydrates at a cobalt phthalocyanine containing chemically modified electrode , 1987 .

[9]  Xueji Zhang,et al.  Cobalt and Copper Hexacyanoferrate Modified Carbon Fiber Microelectrode as an All‐Solid Potentiometric Microsensor for Hydrazine , 2000 .

[10]  J. Zagal,et al.  Electrocatalytic activity of cobalt phthalocyanine CoPc adsorbed on a graphite electrode for the oxidation of reduced L-glutathione (GSH) and the reduction of its disulfide (GSSG) at physiological pH. , 2007, Bioelectrochemistry.

[11]  T. Nyokong,et al.  Novel amperometric glucose biosensor based on an ether-linked cobalt(II) phthalocyanine–cobalt(II) tetraphenylporphyrin pentamer as a redox mediator , 2006 .

[12]  T. Kondo,et al.  Sensitive Electrochemical Detection of Glucose at Glucose Oxidase-Cobalt Phthalocyanine-Modified Boron-Doped Diamond Electrode , 2012 .

[13]  Meihui Chen,et al.  Screen-Printed Carbon Electrodes Modified with Cobalt Phthalocyanine for Selective Sulfur Detection in Cosmetic Products , 2011, International journal of molecular sciences.

[14]  N. Nasirizadeh,et al.  A study of the electrochemical behavior of an oxadiazole derivative electrodeposited on multi-wall carbon nanotube-modified electrode and its application as a hydrazine sensor , 2011 .

[15]  R. Compton,et al.  Voltammetric studies of the redox mediator, cobalt phthalocyanine, with regard to its claimed electrocatalytic properties , 2010 .

[16]  B. Lakard,et al.  Elaboration of ammonia gas sensors based on electrodeposited polypyrrole--cobalt phthalocyanine hybrid films. , 2013, Talanta.

[17]  Craig E. Banks,et al.  The Oxygen Reduction Reaction at Graphene Modified Electrodes , 2014 .

[18]  K. Ozoemena,et al.  Nanostructured cobalt phthalocyanine single-walled carbon nanotube platform: electron transport and electrocatalytic activity on epinephrine , 2008 .

[19]  Xia Sun,et al.  Aptasensor based on the synergistic contributions of chitosan-gold nanoparticles, graphene-gold nanoparticles and multi-walled carbon nanotubes-cobalt phthalocyanine nanocomposites for kanamycin detection. , 2014, The Analyst.

[20]  Kun Wang,et al.  Solid-contact potentiometric sensor for ascorbic acid based on cobalt phthalocyanine nanoparticles as ionophore. , 2005, Talanta.

[21]  Hui Zhang,et al.  An electrochemical biosensor for determination of ascorbic acid by cobalt (II) phthalocyanine–multi-walled carbon nanotubes modified glassy carbon electrode , 2012 .

[22]  Dirk Inzé,et al.  Plant L‐ascorbic acid: chemistry, function, metabolism, bioavailability and effects of processing , 2000 .

[23]  R. Compton,et al.  The use of nanoparticles in electroanalysis: a review , 2006, Analytical and bioanalytical chemistry.

[24]  A. Lever,et al.  Cathodic reduction of oxygen and hydrogen peroxide at cobalt and iron crowned phthalocyanines adsorbed on highly oriented pyrolytic graphite electrodes , 1992 .

[25]  R. Baldwin,et al.  Phthalocyanine-containing chemically modified electrodes for electrochemical detection in liquid chromatography/flow injection systems , 1984 .

[26]  J. F. Rinehart,et al.  THE DETECTION OF SUBCLINICAL SCURVY OR VITAMIN C DEFICIENCY , 1942 .

[27]  Brian J. Birch,et al.  Development of screen-printed carbon electrodes, chemically modified with cobalt phthalocyanine, for electrochemical sensor applications , 1990 .

[28]  A. Shaabani,et al.  A novel bioelectrochemical sensing platform based on covalently attachment of cobalt phthalocyanine to graphene oxide. , 2014, Biosensors & bioelectronics.

[29]  K. Scott,et al.  Electrochemical reduction of oxygen with iron phthalocyanine in neutral media , 2009 .

[30]  K. Ozoemena.  Anodic Oxidation and Amperometric Sensing of Hydrazine at a Glassy Carbon Electrode Modified with Cobalt (II) Phthalocyanine–cobalt (II) Tetraphenylporphyrin (CoPc-(CoTPP)4) Supramolecular Complex , 2006, Sensors (Basel, Switzerland).

[31]  T. Nyokong,et al.  Electrooxidation of hydrazine catalyzed by noncovalently functionalized single-walled carbon nanotubes with CoPc , 2008 .

[32]  John P. Hart,et al.  Prototype, solid-phase, glucose biosensor , 1995 .

[33]  Bruno Jousselme,et al.  Low-platinum and platinum-free catalysts for the oxygen reduction reaction at fuel cell cathodes , 2011 .

[34]  J. Hart,et al.  Electrocatalytic behaviour of citric acid at a cobalt phthalocyanine-modified screen-printed carbon electrode and its application in pharmaceutical and food analysis , 2010, Analytical and bioanalytical chemistry.

[35]  T. Guarr,et al.  Electro-oxidation of hydrazine at electrodes modified with polymeric cobalt phthalocyanine , 1994 .

[36]  J. Hart,et al.  Voltammetric behaviour of ascorbic acid at a graphite-epoxy composite electrode chemically modified with cobalt phthalocyanine and its amperometric determination in multivitamin preparations , 1990 .

[37]  Sanford D Zelnick,et al.  Occupational exposure to hydrazines: treatment of acute central nervous system toxicity. , 2003, Aviation, space, and environmental medicine.

[38]  P. Crouigneau,et al.  Electrocatalytic reduction of oxygen at iron phthalocyanine modified polymer electrodes , 1992 .

[39]  T. Nyokong,et al.  Tetracarboxylic acid cobalt phthalocyanine SAM on gold: Potential applications as amperometric sensor for H2O2 and fabrication of glucose biosensor , 2006 .

[40]  Jing‐Juan Xu,et al.  Determination of Theophylline in Drugs and Tea on Nanosized Cobalt Phthalocyanine Particles Modified Carbon Paste Electrode , 2004 .

[41]  Sibulelo L. Vilakazi,et al.  Nanostructured metallophthalocyanine complexes: synthesis and electrocatalysis , 2012 .

[42]  M. Chicharro,et al.  Flow Injection Analysis of Aziprotryne Using an Electrochemical Sensor Based on Cobalt Phthalocyanine Modified Carbon Paste Electrode , 2002 .

[43]  J. Zagal,et al.  Electrocatalytic oxidation of nitrite on a vitreous carbon electrode modified with cobalt phthalocyanine , 2002 .

[44]  A. Toro‐Labbé,et al.  Comparative study of the electrocatalytic activity of cobalt phthalocyanine and cobalt naphthalocyanine for the reduction of oxygen and the oxidation of hydrazine , 1998 .

[45]  W. Visscher,et al.  The cathodic reduction of oxygen at cobalt phthalocyanine: Influence of electrode preparation on electrocatalysis , 1986 .

[46]  S. Saeger,et al.  An electrocatalytic glucose sensor for in-vivo application. , 1991, Biomedical instrumentation & technology.

[47]  R. Yu,et al.  Pressed-pellet solid potentiometric sensor for ascorbic acid based on derivatives of cobalt(II) phthalocyanine doped with iodine , 1996 .

[48]  A. Shaabani,et al.  Electrocatalytic oxidation of hydrazine at glassy carbon electrode modified with ethylenediamine cellulose immobilized palladium nanoparticles , 2013 .

[49]  Carlos F. Zinola,et al.  Electrocatalysis: Fundamentals and Applications , 2012 .

[50]  J. F. Stevens,et al.  Vitamins C and E: beneficial effects from a mechanistic perspective. , 2011, Free radical biology & medicine.