| Full text | |
| Author(s): |
Sedenho, Graziela C.
[1, 2]
;
De Porcellinis, Diana
[2]
;
Jing, Yan
[3]
;
Kerr, Emily
[3]
;
Mejia-Mendoza, Luis Martin
[3]
;
Vazquez-Mayagoitia, Alvaro
[4]
;
Aspuru-Guzik, Alan
[3, 5, 6]
;
Gordon, Roy G.
[3]
;
Crespilho, Frank N.
[1, 2]
;
Aziz, Michael J.
[2]
Total Authors: 10
|
| Affiliation: | [1] Univ Sao Paulo, Sao Carlos Inst Chem, BR-13560970 Sao Carlos, SP - Brazil
[2] Harvard John A Paulson Sch Engn & Appl Sci, Cambridge, MA 02138 - USA
[3] Harvard Univ, Dept Chem & Chem Biol, Cambridge, MA 02138 - USA
[4] Argonne Natl Lab, Argonne Leadership Comp Facil, 9700 S Cass Ave, Argonne, IL 60439 - USA
[5] Univ Toronto, Dept Comp Sci, Toronto, ON - Canada
[6] Univ Toronto, Dept Chem, Toronto, ON - Canada
Total Affiliations: 6
|
| Document type: | Journal article |
| Source: | ACS APPLIED ENERGY MATERIALS; v. 3, n. 2, p. 1933-1943, FEB 2020. |
| Web of Science Citations: | 0 |
| Abstract | |
Quinones can undergo thermodynamically reversible proton-coupled electron transfer reactions and are being applied as electroactive compounds in aqueous organic batteries. However, the electrochemical reversibility of these compounds is affected not only by their molecular structure but also by the properties of a carbon-based electrode surface. This study combines experimental and theoretical approaches to understand this dependence. We study the electron transfer kinetics of two synthesized quinone derivatives and two commercially available ones with a glassy carbon, a highly ordered pyrolytic graphite, and a high-edge-density graphite electrode (HEDGE). The electrochemical reversibility is notably improved on the HEDGE, which shows a higher density of defects and presents oxygenated functional groups at its surface. The electron transfer kinetics are controlled by adsorbed species onto the HEDGE. Molecular dynamics simulation and quantum mechanics calculations suggest defects with oxygen-containing functional groups, such as C-O and C=O, on HEDGE surfaces drive the interaction with the functional groups of the molecules, during physisorption from van der Waals forces. The presence of sulfonic acid side groups and a greater number of aromatic rings in the molecular structure may contribute to a higher stabilization of quinone derivatives on HEDGEs. We propose that high-performance carbon-based electrodes can be obtained without catalysts for organic batteries, by the engineering of carbon-based surfaces with edge-like defects and oxygenated functional groups. (AU) | |
| FAPESP's process: | 17/15714-0 - Redox flow battery coupled with microbial biofuel cell |
| Grantee: | Graziela Cristina Sedenho |
| Support Opportunities: | Scholarships abroad - Research Internship - Doctorate |
| FAPESP's process: | 13/14262-7 - Nanostructured films from biologically-relevant materials |
| Grantee: | Osvaldo Novais de Oliveira Junior |
| Support Opportunities: | Research Projects - Thematic Grants |
| FAPESP's process: | 15/22973-6 - Development of Microbial Fuel Biocells for Bioproduction and Oxidation of Ethanol |
| Grantee: | Graziela Cristina Sedenho |
| Support Opportunities: | Scholarships in Brazil - Doctorate |