An Aza-Fused π-Conjugated Microporous Framework Catalyzes the Production of Hydrogen Peroxide
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Título: | An Aza-Fused π-Conjugated Microporous Framework Catalyzes the Production of Hydrogen Peroxide |
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Autor/es: | Briega-Martos, Valentín | Ferre-Vilaplana, Adolfo | Peña, Alejandro de la | Segura, José L. | Zamora, Félix | Feliu, Juan M. | 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: | Electrocatalyst | Oxygen reduction | Hydrogen peroxide production | Microporous framework | Conjugated covalent porous polymer |
Área/s de conocimiento: | Química Física |
Fecha de publicación: | 2017 |
Editor: | American Chemical Society |
Cita bibliográfica: | ACS Catalysis. 2017, 7(2): 1015-1024. doi:10.1021/acscatal.6b03043 |
Resumen: | In order to produce hydrogen peroxide in small-scale electrochemical plants, selective catalysts for the oxygen reduction reaction (ORR) toward the desired species are required. Here, we report about the synthesis, characterization, ORR electrochemical behavior, and reaction mechanism of an aza-fused π-conjugated microporous polymer, which presents high selectivity toward hydrogen peroxide. It was synthesized by polycondensation of 1,2,4,5-benzenetetramine tetrahydrochloride and triquinoyl octahydrate. A cobalt-modified version of the material was also prepared by a simple postsynthesis treatment with a Co(II) salt. The characterization of the material is consistent with the formation of a conductive robust porous covalent laminar polyaza structure. The ORR properties of these catalysts were investigated using rotating disk and rotating disk–ring arrangements. The results indicate that hydrogen peroxide is almost exclusively produced at very low overpotentials on these materials. Density functional theory calculations provide key elements to understand the reaction mechanism. It is found that, at the relevant potential for the reaction, half of the nitrogen atoms of the material would be hydrogenated. This hydrogenation process would destabilize some carbon atoms in the lattice and would provide segregated charge. On the destabilized carbon atoms, molecular oxygen would be chemisorbed with the aid of charge transferred from the hydrogenated nitrogen atoms and solvation effects. Due to the low destabilization of the carbon sites, the resulting molecular oxygen chemisorbed state, which would have the characteristics of a superoxide species, would be only slightly stable, promoting the formation of hydrogen peroxide. |
Patrocinador/es: | This work has been financially supported by the MCINN-FEDER (projects CTQ 2016-76221-P, MAT2013-46753-C2-1-P, and MAT2014-52305-P) and Generalitat Valenciana (project PROMETEO/2014/013). |
URI: | http://hdl.handle.net/10045/66568 |
ISSN: | 2155-5435 |
DOI: | 10.1021/acscatal.6b03043 |
Idioma: | eng |
Tipo: | info:eu-repo/semantics/article |
Derechos: | © 2016 American Chemical Society |
Revisión científica: | si |
Versión del editor: | http://dx.doi.org/10.1021/acscatal.6b03043 |
Aparece en las colecciones: | INV - EQSUP - Artículos de Revistas |
Archivos en este ítem:
Archivo | Descripción | Tamaño | Formato | |
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2017_Briega_etal_ACSCatal_final.pdf | Versión final (acceso restringido) | 1,93 MB | Adobe PDF | Abrir Solicitar una copia |
2017_Briega_etal_ACSCatal_preprint.pdf | Preprint (acceso abierto) | 1,84 MB | Adobe PDF | Abrir Vista previa |
2017_Briega_etal_ACSCatal_SI.pdf | Supporting Information | 1,53 MB | Adobe PDF | Abrir Vista previa |
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