Non-aqueous redox flow batteries (RFBs) are promising energy storage devices owing to the broad electrochemical window of organic solvents. Nonetheless, the wide application of these batteries has been limited by the low stability and limited solubility of organic materials, as well as the insufficient ion conductivity of the cell separators in non-aqueous electrolytes. In this study, two viologen analogues with poly­(ethylene glycol) (PEG) tails are designed as anolytes for non-aqueous RFBs. The PEGylation of viologen not only enhances the solubility in acetonitrile but also increases the overall molecular size for alleviated crossover. In addition, a composite nanoporous aramid nanofiber separator, which allows the permeation of supporting ions while inhibiting the crossover of the designer viologens, is developed using a scalable doctor-blading method. Paired with ferrocene, the full organic material-based RFB presents excellent cyclability (500 cycles) with a retention capacity per cycle of 99.93% and an average Coulombic efficiency of 99.3% at a current density of 2.0 mA/cm2. The high performance of the PEGylated viologen validates the potential of the PEGylation strategy for enhanced organic material-based non-aqueous RFBs.

A non-aqueous redox flow battery based on all-PEGylated, metal-free compounds is presented. The PEGylation enhances the stability of the redox-active materials, alleviating crossover by increasing the anolyte and catholyte species’ molecular sizes.

The effects of primary and second coordination spheres on molecular electrocatalysis have been extensively studied, yet investigations of third functional spheres are rarely reported. Here, an electrocatalyst (ZnPEG8T) was developed with a hydrophilic channel as a third functional sphere that facilitates relay proton shuttling to the primary and second coordination spheres for enhanced catalytic CO2 reduction. Using foot‐of‐the‐wave analysis, the ZnPEG8T catalyst displayed CO2‐to‐CO activity (TOFmax) thirty times greater than that of the benchmark catalyst without a third functional sphere. A kinetic isotopic effect (KIE) study, in conjunction with voltammetry and UV/Vis spectroscopy, uncovered that the rate‐limiting step was not the protonation step of the metallocarboxylate intermediate, as observed in many other molecular CO2 reduction electrocatalysts, but rather the replenishment of protons in the proton‐shuttling channel. Controlled‐potential electrolysis using ZnPEG8T displayed a faradaic efficiency of 100 % for CO2‐to‐CO conversion at −2.4 V vs. Fc/Fc+. A Tafel plot was also generated for a comparison to other reported molecular catalysts. This report validates a strategy for incorporating higher functional spheres for enhanced catalytic efficiency in proton‐coupled electron‐transfer reactions.

The remediation of organohalides from water is a challenging process in environment protection and water treatment. Herein, we report a molecular copper(I) complex with two triazole units, CuT2, in a heterogeneous aqueous system that is capable of dechlorinating dichloromethane (CH 2 Cl 2 ) to afford hydrocarbons (methane, ethane, and ethylene). The catalytic performance is evaluated in water and presented high Faradaic efficiency (average 70% CH 4 ) across a range of potentials (−1.1 to −1.6 V vs Ag/AgCl) and high activity (maximum −25.1 mA/cm 2 at −1.6 V vs Ag/AgCl) with a turnover number of 2.0 × 10 7 . The CuT2 catalyst also showed excellent stability for 14 h of constant exposure to CH 2 Cl 2 and 10 h of CH 2 Cl 2 exposure cycling. The control compound, a copper-free triazole unit (T1), was also investigated under the same condition and showed inferior catalytic activity, indicating the importance of the copper center. Plausible catalytic mechanisms are proposed for the formation of C 1 and C 2 products via radical intermediates. Computational studies provided additional insight into the reaction mechanism and the selectivity toward the CH 4 formation. The findings in this study demonstrate that complex CuT2 is an efficient and stable catalyst for the dehalogenation of CH 2 Cl 2 and could potentially be used for the exploration of the removal of halogenated species from aqueous systems.

The control of the second coordination sphere in a coordination complex plays an important role in improving catalytic efficiency. Herein, we report a zinc porphyrin complex ZnPor8T with multiple flexible triazole units comprising the second coordination sphere, as an electrocatalyst for the highly selective electrochemical reduction of carbon dioxide (CO2) to carbon monoxide (CO). This electrocatalyst converted CO2 to CO with a Faradaic efficiency of 99 % and a current density of −6.2 mA cm−2 at −2.4 V vs. Fc/Fc+ in N,N‐dimethylformamide using water as the proton source. Structure‐function relationship studies were carried out on ZnPor8T analogs containing different numbers of triazole units and distinct triazole geometries; these unveiled that the triazole units function cooperatively to stabilize the CO2‐catalyst adduct in order to facilitate intramolecular proton transfer. Our findings demonstrate that incorporating triazole units that function in a cooperative manner is a versatile strategy to enhance the activity of electrocatalytic CO2 conversion.