The electrochemical behavior of cobalt phthalocyanine/platinum as methanol-resistant oxygen-reduction electrocatalysts for DMFC

The electrochemical behavior of cobalt phthalocyanine/platinum as methanol-resistant oxygen-reduction electrocatalyst for DMFC was investigated. Platinum was chemically deposited on the carbon-supported cobalt phthalocyanine (CoPc), and then it was heat-treated in high purity nitrogen at 300 °C, 635 °C and 980 °C. In order to evaluate the electrocatalytic behavior of CoPc-Pt/C, the PtCo/C and Pt/C as reference catalysts were employed. TGA, XRD, EDAX, XPS and electrochemical experiments were used to study the thermal stability, crystal structure, physical characterization and electrochemical behavior of these catalysts. These catalysts exhibited similar electrocatalytic activity for oxygen reaction in 0.5 M H2SO4 solution. In methanol tolerance experiments, Pt/C, PtCo/C and CoPc-Pt/C heated at 980 °C were active for the methanol oxidation reaction (MOR). The presence of Co did not improve resistance to methanol poisoning. However, the CoPc-Pt/C after 300 °C or 635 °C heat-treatment demonstrated significant inactivity for MOR, hence they have a good ability to resist methanol poisoning. The current study indicated that the macrocyclic structure of phthalocyanine is the most important factor to improve the methanol tolerance of CoPc-Pt/C as the oxygen-reduction reaction (ORR) electrocatalyst. The CoPc-Pt based catalyst should be a good alternation for oxygen electro-reduction reaction in DMFC.

[1]  J. Goodenough,et al.  The electroreduction of oxygen on thin films of platinum phthalocyanine in alkaline solutions: Part II. Spectroelectrochemical data and mechanism , 1988 .

[2]  A. Freund,et al.  Improved Pt alloy catalysts for fuel cells , 1996 .

[3]  Kwong-Yu Chan,et al.  Electrocatalytic properties of supported platinum–cobalt nanoparticles with uniform and controlled composition , 2004 .

[4]  R. Jasinski,et al.  A New Fuel Cell Cathode Catalyst , 1964, Nature.

[5]  H. Gasteiger,et al.  Oxygen Reduction on Ru1.92Mo0.08SeO4, Ru/Carbon, and Pt/Carbon in Pure and Methanol‐Containing Electrolytes , 2000 .

[6]  Biswa R. Padhy,et al.  Performance of DMFC with SS 316 bipolar/end plates , 2006 .

[7]  C. Bernard,et al.  Etude de la reduction de l'oxygene sur les phtalocyanines monomeres et polymeres—II: Polyphtalocyanines de fer impregnees sur noir d'acetylene Y , 1974 .

[8]  Weijiang Zhou,et al.  Nano-stuctured Pt–Fe/C as cathode catalyst in direct methanol fuel cell , 2004 .

[9]  H. R. Kunz,et al.  Platinum-macrocycle co-catalysts for the electrochemical oxidation of methanol , 1998 .

[10]  P. Bertrand,et al.  Catalytic activity and stability of heat-treated iron phthalocyanines for the electroreduction of oxygen in polymer electrolyte fuel cells , 1996 .

[11]  C. Roth,et al.  Characterization of different Pt/Metal/Complex catalysts as anode catalysts for the PEM fuel cell , 2005 .

[12]  In-Hwan Oh,et al.  Recent progress in passive direct methanol fuel cells at KIST , 2004 .

[13]  J. Zagal,et al.  Reactivity of immobilized cobalt phthalocyanines for the electroreduction of molecular oxygen in terms of molecular hardness , 2000 .

[14]  J. Goodenough,et al.  Cathodic reduction of oxygen by platinum phthalocyanine thin films , 1984 .

[15]  D. Schlettwein,et al.  Electrochemical reduction of substituted cobalt phthalocyanines adsorbed on graphite , 1998 .

[16]  Ramana G. Reddy,et al.  Effect of channel dimensions and shape in the flow-field distributor on the performance of polymer electrolyte membrane fuel cells , 2003 .

[17]  E. Gonzalez,et al.  Carbon supported Pt-Co alloys as methanol-resistant oxygen-reduction electrocatalysts for direct methanol fuel cells , 2005 .

[18]  G. Tamizhmani,et al.  Physical, Chemical and Electrochemical Characterization of Heat-treated Tetracarboxylic Cobalt Phthalocyanine Adsorbed On Carbon-black As Electrocatalyst for Oxygen Reduction in Polymer Electrolyte Fuel-cells , 1995 .

[19]  Patrick Bertrand,et al.  Heat-treated iron and cobalt tetraphenylporphyrins adsorbed on carbon black: Physical characterization and catalytic properties of these materials for the reduction of oxygen in polymer electrolyte fuel cells , 1996 .

[20]  J. Zeng,et al.  Effects of preparation conditions on performance of carbon-supported nanosize Pt-Co catalysts for methanol electro-oxidation under acidic conditions , 2005 .

[21]  A. Anderson,et al.  Activation energies for oxygen reduction on platinum alloys: theory and experiment. , 2005, The journal of physical chemistry. B.

[22]  E. Oldfield,et al.  UHV, Electrochemical NMR, and Electrochemical Studies of Platinum/Ruthenium Fuel Cell Catalysts , 2002 .

[23]  H. Gasteiger,et al.  Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt oxygen reduction catalysts for PEMFCs , 2005 .

[24]  Jesse S. Wainright,et al.  Microfabricated fuel cells , 2003 .

[25]  Ramana G. Reddy,et al.  Modeling of polymer electrolyte membrane fuel cell with metal foam in the flow-field of the bipolar/end plates , 2003 .

[26]  Emanuel Peled,et al.  Water-neutral micro direct-methanol fuel cell (DMFC) for portable applications , 2003 .

[27]  E. Gonzalez,et al.  Structure and Activity of Carbon-Supported Pt−Co Electrocatalysts for Oxygen Reduction , 2004 .

[28]  H. Reichl,et al.  Development of a planar micro fuel cell with thin film and micro patterning technologies , 2004 .

[29]  A. Krawitz,et al.  Introduction to Diffraction in Materials Science and Engineering , 2001 .

[30]  Kwong-Yu Chan,et al.  Electrocatalytic oxidation of formic acid by Pt/Co nanoparticles , 2001 .

[31]  J. Ulstrup Catalysis of the electrochemical reduction of molecular dioxygen by metal phthalocyanines , 1977 .

[32]  N. Alonso‐Vante,et al.  Electrocatalytic properties of mixed transition metal tellurides (Chevrel-phases) for oxygen reduction , 1995 .

[33]  K. Eguchi,et al.  Selective removal of NO by absorption in mixed oxide catalysts , 1996 .

[34]  T. Osaka,et al.  MEMS-based design and fabrication of a new concept micro direct methanol fuel cell (μ-DMFC) , 2004 .

[35]  Xiang Zhang,et al.  A micro methanol fuel cell operating at near room temperature , 2003 .

[36]  J. Goodenough,et al.  Porous carbon anodes for the direct methanol fuel cell—I. The role of the reduction method for carbon supported platinum electrodes , 1990 .

[37]  J. Zagal,et al.  Linear versus volcano correlations between electrocatalytic activity and redox and electronic properties of metallophthalocyanines , 1998 .