Studies of oxygen reduction reaction active sites and stability of nitrogen-modified carbon composite catalysts for PEM fuel cells

Abstract A non-precious nitrogen-modified carbon composite (NMCC) catalyst is synthesized by the pyrolysis of cobalt, iron–ethylenediamine–chelate complexes on silica followed by chemical and pyrolysis treatments. Pyrolysis temperature and time have a remarkable impact on the content and the type of the nitrogen-containing functional groups in the NMCC catalysts, which affect their catalytic activity and stability. Based on the analysis of the nitrogen functional groups before and after the stability tests, the ORR active sites of the NMCC catalysts are proposed to be pyridinic-N and quaternary-N functional groups. However the pyridinic-N group is not stable in the acidic environment due to the protonation reaction.

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

[2]  Lei Zhang,et al.  Progress in preparation of non-noble electrocatalysts for PEM fuel cell reactions , 2006 .

[3]  Kiyoyuki Terakura,et al.  Carbon Alloy Catalysts: Active Sites for Oxygen Reduction Reaction , 2008 .

[4]  Branko N. Popov,et al.  Development of non-precious metal oxygen-reduction catalysts for PEM fuel cells based on N-doped ordered porous carbon , 2009 .

[5]  J. Riga,et al.  Oxygen reduction in acidic media catalyzed by pyrolyzed cobalt macrocycles dispersed on an active carbon: The importance of the content of oxygen surface groups on the evolution of the chelate structure during the heat treatment , 1998 .

[6]  K. Wiesener,et al.  N4-chelates as electrocatalyst for cathodic oxygen reduction , 1986 .

[7]  Lei Zhang,et al.  Oxygen reduction reaction (ORR) catalyzed by carbon-supported cobalt polypyrrole (Co-PPy/C) electrocatalysts , 2009 .

[8]  Jong-Won Lee,et al.  Development of high performance carbon composite catalyst for oxygen reduction reaction in PEM Proton Exchange Membrane fuel cells , 2008 .

[9]  Thomas E. Wood,et al.  Non-precious metal oxygen reduction catalyst for PEM fuel cells based on nitroaniline precursor ☆ , 2008 .

[10]  Ernest Yeager,et al.  Electrocatalysts for O2 reduction , 1984 .

[11]  P. Ross,et al.  Surface science studies of model fuel cell electrocatalysts , 2002 .

[12]  Sebastian Fiechter,et al.  Nature of the Catalytic Centers of Porphyrin-Based Electrocatalysts for the ORR: A Correlation of Kinetic Current Density with the Site Density of Fe−N4 Centers , 2008 .

[13]  F. Jaouen,et al.  Increasing the activity of Fe/N/C catalysts in PEM fuel cell cathodes using carbon blacks with a high-disordered carbon content , 2008 .

[14]  Scott Calabrese Barton,et al.  Non-precious oxygen reduction catalysts prepared by high-pressure pyrolysis for low-temperature fuel cells , 2009 .

[15]  Patrick Bertrand,et al.  O-2 reduction in PEM fuel cells: Activity and active site structural information for catalysts obtained by the pyrolysis at high temperature of Fe precursors , 2000 .

[16]  Edward F. Holby,et al.  Instability of Supported Platinum Nanoparticles in Low-Temperature Fuel Cells , 2007 .

[17]  Stephen Maldonado,et al.  Direct preparation of carbon nanofiber electrodes via pyrolysis of iron(II) phthalocyanine: Electrocatalytic aspects for oxygen reduction , 2004 .

[18]  W. Schuhmann,et al.  Electrocatalytic Activity and Stability of Nitrogen-Containing Carbon Nanotubes in the Oxygen Reduction Reaction , 2009 .

[19]  Umit S. Ozkan,et al.  The role of nanostructure in nitrogen-containing carbon catalysts for the oxygen reduction reaction , 2006 .

[20]  Stephen A. Morin,et al.  Structure, composition, and chemical reactivity of carbon nanotubes by selective nitrogen doping , 2006 .

[21]  Kateryna Artyushkova,et al.  Polyaniline-derived Non-Precious Catalyst for the Polymer Electrolyte Fuel Cell Cathode , 2008 .

[22]  H. Gasteiger,et al.  Just a Dream—or Future Reality? , 2009, Science.

[23]  H. Binder,et al.  Mechanism of the electrocatalytic reduction of oxygen on metal chelates , 1973 .

[24]  Mahlon Wilson,et al.  Scientific aspects of polymer electrolyte fuel cell durability and degradation. , 2007, Chemical reviews.

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

[26]  Jun Shen,et al.  A review of PEM fuel cell durability: Degradation mechanisms and mitigation strategies , 2008 .

[27]  Kiyoyuki Terakura,et al.  X-ray absorption analysis of nitrogen contribution to oxygen reduction reaction in carbon alloy cathode catalysts for polymer electrolyte fuel cells , 2009 .

[28]  Freek Kapteijn,et al.  Evolution of nitrogen functionalities in carbonaceous materials during pyrolysis , 1995 .

[29]  Wenhua Geng,et al.  Analysis of hydrothermally-treated and weathered coals by X-ray photoelectron spectroscopy (XPS) , 2009 .

[30]  H. Tributsch,et al.  Catalysts for the Oxygen Reduction from Heat-Treated Iron(III) Tetramethoxyphenylporphyrin Chloride: Structure and Stability of Active Sites , 2003 .