期刊
ACS APPLIED ENERGY MATERIALS
卷 3, 期 9, 页码 8833-8841出版社
AMER CHEMICAL SOC
DOI: 10.1021/acsaem.0c01336
关键词
Marcus-Hush theory; kinetic constant; diquat derivatives; Shannon entropy; reorganization energy
资金
- DGTIC-UNAM [LANCAD-UNAM-DGTIC-022]
- CONACyT-SENER-Fondo de Sustentabilidad Energetica [292862]
An electrochemical analysis strategy based on the Marcus-Hush approximation is presented to analyze the kinetic component of organic redox flow battery (RFB) electrolytes. The procedure was applied to aqueous solutions of methyl viologen (MV) and 2,2'-bipyridyl (diquat, DQ) derivatives as model redox-active electrolytes; although these systems are promising negolyte candidates in organic RFBs, their electrode kinetics continues to be unclear. For compound MV, the voltammetric analysis revealed an adsorption process of electrogenerated species to the glassy carbon electrode surface, so its electron transfer rate constant k(s) should not be estimated by applying outer sphere electron transfer formulations. For the remaining compounds studied, experimental k(s) values were obtained and they range from 0.22 to 0.62 cm s(-1). Quantum chemical modeling was applied not only to decipher properties of the adsorption process of the MV structure but also to rationalize the kinetic differences in compounds studied through their total and inner reorganization energies. This experimental and theoretical approach allowed elucidation of the kinetic component of compounds studied, revealing that k(s) values for MV and DQ compound derivatives should not exhibit the reported differences of at least one order of magnitude. Finally, the experimental k(s) value (0.62 cm s(-1)) obtained for compound 5,5'-DMDQ is the largest value reported to date in the literature of aqueous organic RFBs, which makes it a strong anolyte candidate.
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