Theoretical Predictions Concerning Oxygen Reduction on Nitrided Graphite Edges and a Cobalt Center Bonded to Them

Density functional theory and a linear Gibbs free energy relationship are employed in a theoretical investigation of catalytic properties of cobalt−graphite−nitride systems for O2 reduction to hydrogen peroxide and water. Nitrided graphite edges, with N atoms substituting one or two CH groups, are modeled to establish some of the effects of N on edges with and without Co added. The calculations show that a bare graphite edge with one N atom, which the calculations indicate is not hydrogenated at potentials greater than 0.3 V, is not active for O2 reduction because OOH bonds too weakly. At potentials lower than 0.3 V, for which N is hydrogenated, making it a radical center, the NH edge is not active for O2 reduction because OOH bonds too strongly, resulting in a high overpotential for its reduction to H2O2 on this site. Over a Co site bridging two N substituting for CH on an edge, the onset formation potential for OOH(ads) is about 0.4 V for Co0, 0.8 V for CoII in the form of Co(OH)2, 0.7 V for CoII in the...

[1]  R. Gómez,et al.  Effect of Temperature on Hydrogen Adsorption on Pt(111), Pt(110), and Pt(100) Electrodes in 0.1 M HClO4 , 2004 .

[2]  Titus V. Albu,et al.  Catalytic effect of platinum on oxygen reduction : An ab initio model including electrode potential dependence , 2000 .

[3]  G. Tayhas R. Palmore,et al.  Electro-enzymatic reduction of dioxygen to water in the cathode compartment of a biofuel cell , 1999 .

[4]  V. S. Bagotzky,et al.  Electrocatalysis of the oxygen reduction process on metal chelates in acid electrolyte , 1978 .

[5]  Patrick Bertrand,et al.  Molecular Oxygen Reduction in PEM Fuel Cells: Evidence for the Simultaneous Presence of Two Active Sites in Fe-Based Catalysts , 2002 .

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

[7]  Elizabeth J. Biddinger,et al.  Oxygen reduction reaction catalysts prepared from acetonitrile pyrolysis over alumina-supported metal particles. , 2006, The journal of physical chemistry. B.

[8]  A. Anderson,et al.  Theory for the Potential Shift for OH ads Formation on the Pt Skin on Pt3Cr ( 111 ) in Acid , 2004 .

[9]  R. Pierattelli,et al.  Reduction thermodynamics of the T1 Cu site in plant and fungal laccases , 2005, JBIC Journal of Biological Inorganic Chemistry.

[10]  Alfred B. Anderson,et al.  O2 reduction on graphite and nitrogen-doped graphite: experiment and theory. , 2006, The journal of physical chemistry. B.

[11]  E. Yeager,et al.  Transition metal macrocycles supported on high area carbon: pyrolysis-mass spectrometry studies , 1986 .

[12]  H. Gasteiger,et al.  Effect of temperature on surface processes at the Pt(111)-liquid interface: Hydrogen adsorption, oxide formation and CO oxidation , 1999 .

[13]  Francisco A. Uribe,et al.  A study of polymer electrolyte fuel cell performance at high voltages. Dependence on cathode catalyst layer composition and on voltage conditioning , 2002 .

[14]  D. Ohms,et al.  Investigation of the influence of thermal treatment on the properties of carbon materials modified by N4-chelates for the reduction of oxygen in acidic media , 1989 .

[15]  Ernest Yeager,et al.  Heat-treated polyacrylonitrile-based catalysts for oxygen electroreduction , 1989 .

[16]  N. Marković,et al.  Surface Composition Effects in Electrocatalysis: Kinetics of Oxygen Reduction on Well-Defined Pt3Ni and Pt3Co Alloy Surfaces , 2002 .

[17]  A. Hughes,et al.  A comparison of weak molecular adsorption of organic molecules on clean copper and platinum surfaces , 1984 .

[18]  C. E. Mooney,et al.  Energetics for the desorption of hydroxyl radicals from a platinum surface , 1993 .

[19]  U. Ozkan,et al.  Characterization of the Iron Phase in CNx-Based Oxygen Reduction Reaction Catalysts , 2007 .

[20]  X. Xia,et al.  Adsorption of water at Pt(111) electrode in HClO4 solutions. The potential of zero charge , 1996 .

[21]  J.A.R. van Veen,et al.  On the effect of a heat treatment on the structure of carbon-supported metalloporphyrins and phthalocyanines , 1988 .

[22]  R. Gómez,et al.  Thermodynamic analysis of the temperature dependence of OH adsorption on Pt(111) and Pt(100) electrodes in acidic media in the absence of specific anion adsorption. , 2006, The journal of physical chemistry. B.

[23]  Sanjeev Mukerjee,et al.  Role of Structural and Electronic Properties of Pt and Pt Alloys on Electrocatalysis of Oxygen Reduction An In Situ XANES and EXAFS Investigation , 1995 .

[24]  Reyimjan A. Sidik,et al.  Oxygen Electroreduction on FeII and FeIII Coordinated to N4 Chelates. Reversible Potentials for the Intermediate Steps from Quantum Theory , 2004 .

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

[26]  Piotr Zelenay,et al.  A class of non-precious metal composite catalysts for fuel cells , 2006, Nature.

[27]  N. Guillet,et al.  Electrogeneration of Hydrogen Peroxide in Acid Medium using Pyrolyzed Cobalt-based Catalysts: Influence of the Cobalt Content on the Electrode Performance , 2006 .

[28]  B. Conway,et al.  Energetics of an electrochemical reaction derived from the intersection of tafel lines determined at different temperatures , 1989 .