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Electrocatalytic water oxidation reaction promoted by cobalt-Prussian blue and its thermal decomposition product under mild conditions

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Autor(es):
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Zambiazi, Priscilla J. [1] ; Aparecido, Gabriel de O. [1] ; Ferraz, Thiago V. de B. [1] ; Skinner, William S. J. [1, 2] ; Yoshimura, Rafael G. [1] ; Moreira, Daniel E. B. [1] ; Germscheidt, Rafael L. [1] ; Nascimento, Lucas L. [3] ; Patrocinio, Antonio Otavio T. [3] ; Formiga, Andre L. B. [1] ; Bonacin, Juliano A. [1]
Número total de Autores: 11
Afiliação do(s) autor(es):
[1] Univ Estadual Campinas, Inst Chem, BR-13083970 Campinas, SP - Brazil
[2] Imperial Coll London, Dept Mat, London - England
[3] Univ Fed Uberlandia, Inst Chem, Lab Photochem & Mat Sci, BR-38400902 Uberlandia, MG - Brazil
Número total de Afiliações: 3
Tipo de documento: Artigo Científico
Fonte: DALTON TRANSACTIONS; v. 49, n. 45, p. 16488-16497, DEC 7 2020.
Citações Web of Science: 0
Resumo

Cobalt-Prussian blue analogues are remarkable catalysts for the oxygen evolution reaction (water oxidation) under mild conditions such as neutral pH. Although there are extensive reports in the literature about the application of these catalysts in water oxidation (the limiting step for hydrogen evolution), some limitations must be overcome in terms of improving the turnover frequency, oxygen production, long term stability, and elucidation of the mechanism. Another important feature to consider is the industrial processability of electrolytic cells for water splitting. For these reasons, we have reported herein a comparison of the electrochemical and chemical properties of three catalysts produced from cobalt-Prussian blue. Co-Co PBA 60 refers to cobalt-Prussian blue heated up to 60 degrees C with a high content of water. Co-Co PBA 200 is the same starting material but heated up to 200 degrees C with a low water content. Finally, Co3O4 is a thermal decomposition product obtained from heating cobalt-Prussian blue up to 400 degrees C. Although Co-Co PBA 60 has a higher overpotential for water oxidation than Co-Co PBA 200, this catalyst is kinetically faster than Co PBA 200. It is suggested that the water coordinated to Co2+ in Co-Co PBA 60 can accelerate the reaction and that there is a balance between the thermodynamic and kinetic characteristics for determining the final properties of the catalyst at pH = 7. Another important observation is that the Co3O4 catalyst has the best performance among the considered catalysts with the highest TON and TOF. This suggests that the different mechanisms and surface effects demonstrated by the Co3O4 catalyst are more conducive to efficient water oxidation than those of Prussian blue. Further studies concerning the effect of water and surface on these catalysts under mild conditions are essential to gain a better understanding of the mechanism of water oxidation and to advance the development of new catalysts. (AU)

Processo FAPESP: 19/20688-3 - Estudo das propriedades de nanofios de análogos de Azul da Prússia para oxidação de água
Beneficiário:Daniel Esteves Bessa Moreira
Modalidade de apoio: Bolsas no Brasil - Mestrado
Processo FAPESP: 18/25092-9 - Estudo de mecanismo de oxidação de água por catalisadores com estruturas análogas ao do azul da Prússia
Beneficiário:Rafael Lavagnolli Germscheidt
Modalidade de apoio: Bolsas no Brasil - Doutorado Direto
Processo FAPESP: 13/22127-2 - Desenvolvimento de novos materiais estratégicos para dispositivos analíticos integrados
Beneficiário:Lauro Tatsuo Kubota
Modalidade de apoio: Auxílio à Pesquisa - Temático
Processo FAPESP: 17/23960-0 - Estudo de mecanismo de oxidação de água por catalisadores operando em pH=7 e sua incorporação em eletrodos impressos em 3D
Beneficiário:Juliano Alves Bonacin
Modalidade de apoio: Auxílio à Pesquisa - Regular