Electrosynthesis of Verdoheme and Biliverdin Derivatives Following Enzymatic Pathways.

Artificial syntheses of biologically active molecules have been fruitful in many bioinspired catalysis applications. Specifically, verdoheme and biliverdin, bearing polypyrrole frameworks, have inspired catalyst designs to address energy and environmental challenges. Despite remarkable progress in benchtop synthesis of verdoheme and biliverdin derivatives, all reported syntheses, starting from metalloporphyrins or inaccessible biliverdin precursors, require multiple steps to achieve the final desired products. Additionally, such synthetic procedures use multiple reactants/redox agents and involve multistep purification/extraction processes that often lower the yield. However, in a single step using atmospheric oxygen, heme oxygenases selectively generate verdoheme or biliverdin from heme. Motivated by such enzymatic pathways, we report a single-step electrosynthesis of verdoheme or biliverdin derivatives from their corresponding meso-aryl-substituted metalloporphyrin precursors. Our electrosynthetic methods have produced a copper-coordinating verdoheme analog in >80% yield at an applied potential of 0.65 V vs ferrocene/ferrocenium in air-exposed acetonitrile solution with a suitable electrolyte. These electrosynthetic routes reached a maximum product yield within 8 h of electrolysis at room temperature. The major products of verdoheme and biliverdin derivatives were isolated, purified, and characterized using electrospray mass spectrometry, absorption spectroscopy, cyclic voltammetry, and nuclear magnetic resonance spectroscopy techniques. Furthermore, X-ray crystallographic data were collected for select cobalt (Co)- and Cu-chelating verdoheme and metal-free biliverdin products. Electrosynthesis routes for the selective modification at the macrocycle ring in a single step are not known yet, and therefore, we believe that this report would advance the scopes of electrosynthesis strategies.

Hydrodechlorination of Dichloromethane by a Metal-Free Triazole-Porphyrin Electrocatalyst: Demonstration of Main-Group Element Electrocatalysis*.

In this work, the electrocatalytic reduction of dichloromethane (CH2 Cl2 ) into hydrocarbons involving a main group element-based molecular triazole-porphyrin electrocatalyst H2PorT8 is reported. This catalyst converted CH2 Cl2 in acetonitrile to various hydrocarbons (methane, ethane, and ethylene) with a Faradaic efficiency of 70 % and current density of -13 mA cm-2 at a potential of -2.2 V vs. Fc/Fc+ using water as a proton source. The findings of this study and its mechanistic interpretations demonstrated that H2PorT8 was an efficient and stable catalyst for the hydrodechlorination of CH2 Cl2 and that main group catalysts could be potentially used for exploring new catalytic reaction mechanisms.

Electrocatalytic Dechlorination of Dichloromethane in Water Using a Heterogenized Molecular Copper Complex.

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 (CH2Cl2) to afford hydrocarbons (methane, ethane, and ethylene). The catalytic performance is evaluated in water and presented high Faradaic efficiency (average 70% CH4) across a range of potentials (-1.1 to -1.6 V vs Ag/AgCl) and high activity (maximum -25.1 mA/cm2 at -1.6 V vs Ag/AgCl) with a turnover number of 2.0 × 107. The CuT2 catalyst also showed excellent stability for 14 h of constant exposure to CH2Cl2 and 10 h of CH2Cl2 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 C1 and C2 products via radical intermediates. Computational studies provided additional insight into the reaction mechanism and the selectivity toward the CH4 formation. The findings in this study demonstrate that complex CuT2 is an efficient and stable catalyst for the dehalogenation of CH2Cl2 and could potentially be used for the exploration of the removal of halogenated species from aqueous systems.

Enhanced Electrocatalytic Activity of a Zinc Porphyrin for CO2 Reduction: Cooperative Effects of Triazole Units in the Second Coordination Sphere.

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.

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.

Enhanced Molecular CO2 Electroreduction Enabled by a Flexible Hydrophilic Channel for Relay Proton Shuttling.

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.

A pH-Neutral, Aqueous Redox Flow Battery with a 3600-Cycle Lifetime: Micellization-Enabled High Stability and Crossover Suppression.

Redox-flow batteries (RFBs) are a highly promising large-scale energy storage technology for mitigating the intermittent nature of renewable energy sources. Here, the design and implementation of a micellization strategy in an anthraquinone-based, pH-neutral, nontoxic, and metal-free aqueous RFB is reported. The micellization strategy (1) improves stability by protecting the redox-active anthraquinone core with a hydrophilic poly(ethylene glycol) shell and (2) increases the overall size to mitigate the crossover issue through a physical blocking mechanism. Paired with a well-established potassium ferrocyanide catholyte, the micelle-based RFB displayed an excellent capacity retention of 90.7 % after 3600 charge/discharge cycles (28.3 days), corresponding to a capacity retention of 99.67 % per day and 99.998 % per cycle. The mechanistic studies of redox-active materials were also conducted and indicated the absence of side reactions commonly observed in other anthraquinone-based RFBs. The outstanding performance of the RFB demonstrates the effectiveness of the micellization strategy for enhancing the performance of organic material-based aqueous RFBs.

PEGylation-Enabled Extended Cyclability of a Non-aqueous Redox Flow Battery.

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.