High-Voltage Catholyte for High-Energy-Density Nonaqueous Redox Flow Battery.

Redox flow batteries (RFBs) with high energy densities are essential for efficient and sustainable long-term energy storage on a grid scale. To advance the development of nonaqueous RFBs with high energy densities, a new organic RFB system employing a molecularly engineered tetrathiafulvalene derivative ((PEG3/PerF)-TTF) as a high energy density catholyte was developed. When paired with a lithium metal anode, the two-electron-active (PEG3/PerF)-TTF catholyte produced a cell voltage of 3.56 V for the first reduction and 3.92 V for the second reduction process. In cyclic voltammetry and flow cell tests, the redox chemistry exhibited excellent cycling stability. The Li|(PEG3/PerF)-TTF batteries, with concentrations of 0.1 M and 0.5 M, demonstrated capacity retention rates of ~94% (99.87% per cycle, 97.52% per day) and 90% (99.93% per cycle, 99.16% per day), and the average Coulombic efficiencies of 99.38% and 98.35%, respectively. The flow cell achieved a high power density of 129 mW/cm2. Furthermore, owing to the high redox potential and solubility of (PEG3/PerF)-TTF, the flow cell attained a high operational energy density of 72 Wh/L (100 Wh/L theoretical). A 0.75 M flow cell exhibited an even higher operational energy density of 96 Wh/L (150 Wh/L theoretical).

Molecular Cu Electrocatalyst Escalates Ambient Perfluorooctanoic Acid Degradation.

Groundwater reservoirs contaminated with perfluoroalkyl and polyfluoroalkyl substances (PFASs) need purifying remedies. Perfluorooctanoic acid (PFOA) is the most abundant PFAS in drinking water. Although different degradation strategies for PFOA have been explored, none of them disintegrates the PFOA backbone rapidly under mild conditions. Herein, we report a molecular copper electrocatalyst that assists in the degradation of PFOA up to 93% with a 99% defluorination rate within 4 h of cathodic controlled-current electrolysis. The current-normalized pseudo-first-order rate constant has been estimated to be quite high for PFOA decomposition (3.32 L h-1 A-1), indicating its fast degradation at room temperature. Furthermore, comparatively, rapid decarboxylation over the first 2 h of electrolysis has been suggested to be the rate-determining step in PFOA degradation. The related Gibbs free energy of activation has been calculated as 22.6 kcal/mol based on the experimental data. In addition, we did not observe the formation of short-alkyl-chain PFASs as byproducts that are typically found in chain-shortening PFAS degradation routes. Instead, free fluoride (F-), trifluoroacetate (CF3COO-), trifluoromethane (CF3H), and tetrafluoromethane (CF4) were detected as fragmented PFOA products along with the evolution of CO2 using gas chromatography (GC), ion chromatography (IC), and gas chromatography-mass spectrometry (GC-MS) techniques, suggesting comprehensive cleavage of C-C bonds in PFOA. Hence, this study presents an effective method for the rapid degradation of PFOA into small ions/molecules.

Synthesis and Characterization of ZnO-CeO2 Nanocomposite with Enhanced UV-Light-Driven Photocatalytic Dye Degradation of Rhodamine-B.

ZnO-CeO2 nanocomposite was synthesized by co-precipitation and reverse micelle methods, which show rod-shaped morphologies. In co-precipitation method, the nanocomposite has uniform rodshaped structure, whereas in reverse micelle method rods like structures are made up of spherical shaped nanoparticles. The photocatalytic dye degradation of rhodamine-B (RhB) has been examined using ZnO-CeO2 nanocomposite at room temperature. The photodegradation rates of catalysts in co-precipitation and reverse micelle methods were observed as 0.026 min-1 and 0.042 min-1, respectively.

Development of high-voltage and high-energy membrane-free nonaqueous lithium-based organic redox flow batteries.

Lithium-based nonaqueous redox flow batteries (LRFBs) are alternative systems to conventional aqueous redox flow batteries because of their higher operating voltage and theoretical energy density. However, the use of ion-selective membranes limits the large-scale applicability of LRFBs. Here, we report high-voltage membrane-free LRFBs based on an all-organic biphasic system that uses Li metal anode and 2,4,6-tri-(1-cyclohexyloxy-4-imino-2,2,6,6-tetramethylpiperidine)-1,3,5-triazine (Tri-TEMPO), N-propyl phenothiazine (C3-PTZ), and tris(dialkylamino)cyclopropenium (CP) cathodes. Under static conditions, the Li||Tri-TEMPO, Li||C3-PTZ, and Li||CP batteries with 0.5 M redox-active material deliver capacity retentions of 98%, 98%, and 92%, respectively, for 100 cycles over ~55 days at the current density of 1 mA/cm2 and a temperature of 27 °C. Moreover, the Li||Tri-TEMPO (0.5 M) flow battery delivers an initial average cell discharge voltage of 3.45 V and an energy density of ~33 Wh/L. This flow battery also demonstrates 81% of capacity for 100 cycles over ~45 days with average Coulombic efficiency of 96% and energy efficiency of 82% at the current density of 1.5 mA/cm2 and at a temperature of 27 °C.