This study concerns the development of sustainable design strategies of aqueous electrolytes for redox flow batteries using redox-active organic materials. A green spontaneous grafting reaction occurs between a redox-active organic radical and an electrochemically activated structural modifier at room temperature through a simple mixing step. Then, a physical mixing method is used to formulate a structured aqueous electrolyte and enables aqueous solubilization of the organic solute from below 0.5 to 1.5 m beyond the conventional dissolution limit. The as-obtained concentrated mixture can be readily used as catholyte for a redox flow battery. A record high discharge cell voltage (1.6 V onset output voltage) in aqueous non-hybrid flow cell is attained by using the studied electrolytes.
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http://dx.doi.org/10.1002/cssc.202201993 | DOI Listing |
J Phys Chem Lett
January 2025
School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram, Thiruvananthapuram, Kerala 695551, India.
Electronic coupling between individual redox units in a molecular assembly dictates their charge transfer efficacy. Being a well-defined crystalline structure, the metal-organic framework (MOF) ensures proper positioning of redox-active moieties and provides a unique platform to unveil their charge transfer dynamics and quantification with structural relationships. Here, we demonstrate a novel redox-active MOF with near-infrared through-space intervalence charge transfer by introducing a mixed valence state inside redox-active thiazolothiazole-based ligands (DPTTZ) upon photo- or electrochemical reduction.
View Article and Find Full Text PDFSmall Methods
January 2025
Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, Uttar Pradesh, 208016, India.
Molecular electronics exhibiting resistive-switching memory features hold great promise for the next generation of digital technology. In this work, electrosynthesis of ruthenium polypyridyl nanoscale oligomeric films is demonstrated on an indium tin oxide (ITO) electrode followed by an ITO top contact deposition yielding large-scale (junction area = 0.7 × 0.
View Article and Find Full Text PDFChemistry
January 2025
Justus-Liebig Universität, Institut für Organische Chemie, Heinrich-Buff-Ring 17, 35392, Giessen, GERMANY.
Aryl diazenes, particularly azobenzenes (AB), represent a versatile class of compounds with significant historical and practical relevance, ranging from dyes to molecular machines, solar thermal and electrochemical storage. Their oxygen-substituted counterparts, azoxybenzenes (AOB), share structural similarities but have been less explored, especially in energy storage applications. This study investigates the redox properties of AOB, comparing them to AB, and evaluates their potential as redox-active materials for energy storage systems.
View Article and Find Full Text PDFAcc Chem Res
January 2025
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.
ConspectusIn recent years, our research group has dedicated significant effort to the field of asymmetric organometallic electrochemical synthesis (AOES), which integrates electrochemistry with asymmetric transition metal catalysis. On one hand, we have rationalized that organometallic compounds can serve as molecular electrocatalysts (mediators) to reduce overpotentials and enhance both the reactivity and selectivity of reactions. On the other hand, the conditions for asymmetric transition metal catalysis can be substantially improved through electrochemistry, enabling precise modulation of the transition metal's oxidation state by controlling electrochemical potentials and regulating the electron transfer rate via current adjustments.
View Article and Find Full Text PDFChemistry
January 2025
University of Turku: Turun Yliopisto, Department of Mechanical and Materials Engineering, FINLAND.
Viologen derivatives feature two reversible one-electron redox processes and have been extensively utilized in aqueous organic flow batteries (AOFBs). However, the early variant, methyl viologen (MVi), exhibits low stability in aqueous electrolytes, restricting its practical implementation in AOFB technology. In this context, leveraging the tunability of organic molecules, various substituents have been incorporated into the viologen core to achieve better stability, lower redox potential, and improved solubility.
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