| Texto completo | |
| Autor(es): |
Rodrigues, Matheus G. B.
;
de Melo, Andre L. Pesquero
;
Coutinho-Neto, Mauricio D.
;
Angelucci, Camilo A.
Número total de Autores: 4
|
| Tipo de documento: | Artigo Científico |
| Fonte: | CHEMCATCHEM; v. N/A, p. 9-pg., 2024-12-31. |
| Resumo | |
In this study, we investigate the indirect electro-oxidation of benzyl alcohol (BA) using the copper/TEMPO catalytic system, which combines copper complexes with 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) in an anaerobic medium. We reexamine the impact of bpy ligand proportions, exploring ratios of 1:1, 2:1, 3:1, and 4:1 on catalytic activity. Cyclic voltammetry and visible spectroscopy reveal distinct electrochemical characteristics and complex formations at different bpy ratios. Simulations uncover intricate energy equilibria involving ion coordination, varying with oxidation state, and bpy proportion. Theoretical and experimental spectra align, supporting the proposed structures. The Br & oslash;nsted base, triethylamine (TEA), essential in this anaerobic system, shows different voltammetric profiles with each ligand ratio, revealing key interactions with bpy complexes. In the presence of BA, the 1:1 and 2:1 ratios exhibit indirect catalytic activity, with the 2:1 ratio yielding significantly higher current densities. This establishes a new optimal condition where [Cu(bpy)2]2+$[{\rm Cu(bpy)}_{2}]{}<^>{2+}$ formed in a 2:1 stoichiometry demonstrates superior activity with a lower redox potential, while maintaining labile coordination points for necessary interactions. Theoretical results also indicate weaker TEMPO coordination to [Cu(bpy)2]2+$[{\rm Cu(bpy)}_{2}]{}<^>{2+}$. (AU) | |
| Processo FAPESP: | 18/10292-2 - Espectroscopia Raman amplificada por superfície (SERS) aplicado a processos eletroquímicos. |
| Beneficiário: | Camilo Andrea Angelucci |
| Modalidade de apoio: | Auxílio à Pesquisa - Regular |
| Processo FAPESP: | 22/11345-8 - Processo de transformação eletrocatalítica de polióis assistido por mediadores redox |
| Beneficiário: | Camilo Andrea Angelucci |
| Modalidade de apoio: | Auxílio à Pesquisa - Regular |