Understanding the chemisorption-based activation mechanism of the oxygen reduction reaction on nitrogen-doped graphitic materials

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Título: Understanding the chemisorption-based activation mechanism of the oxygen reduction reaction on nitrogen-doped graphitic materials
Autor/es: Ferre-Vilaplana, Adolfo | Herrero, Enrique
Grupo/s de investigación o GITE: Electroquímica de Superficies
Centro, Departamento o Servicio: Universidad de Alicante. Departamento de Química Física | Universidad de Alicante. Instituto Universitario de Electroquímica
Palabras clave: Graphene | Oxygen reduction reaction | Nitrogen | Edges
Área/s de conocimiento: Química Física
Fecha de publicación: 20-jun-2016
Editor: Elsevier
Cita bibliográfica: Electrochimica Acta. 2016, 204: 245-254. doi:10.1016/j.electacta.2016.04.039
Resumen: To optimize nitrogen-doped graphitic materials as metal-free catalysts for the oxygen reduction reaction mechanisms have to be better understood. Here, the role played by pyridinic nitrogen-dopants in the chemisorption-based activation of the target reaction is revealed. The study is centered on the monodentate chemisorption of molecular oxygen as the first step of the process. Several configurations of unclustrered nitrogen dopants in which there was always a nitrogen dopant in the edge of the material were tested using DFT. A clearly favorable chemisorbed state for molecular oxygen was found when the pyridinic nitrogen-dopant is hydrogenated and located at an armchair edge. The found chemisorbed state is further favored by additional available charge. By contrast, the chemisorbed state of oxygen is much less favorable when the hydrogenated pyridinic nitrogen-dopants are located at zigzag edges. Moreover, it was found that the charge involved in the hydrogenation of pyridinic nitrogen-dopants remains segregated, becoming available for reduction processes. Detailed reasons for the described facts are given, and an integrated model for the target activation mechanism is proposed including graphitic nitrogen-dopants effects.
Patrocinador/es: This work has been financially supported by the MICINN (Spain) (project 2013-44083-P) and Generalitat Valenciana (project PROMETEOII/2014/013).
URI: http://hdl.handle.net/10045/54452
ISSN: 0013-4686 (Print) | 1873-3859 (Online)
DOI: 10.1016/j.electacta.2016.04.039
Idioma: eng
Tipo: info:eu-repo/semantics/article
Derechos: © 2016 Elsevier Ltd.
Revisión científica: si
Versión del editor: http://dx.doi.org/10.1016/j.electacta.2016.04.039
Aparece en las colecciones:INV - EQSUP - Artículos de Revistas

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