Organic Redox Research Articles

Use of Intramolecular Quinol Redox Couples to Facilitate the Catalytic Transformation of O2 and O2-Derived Species.

ConspectusThe redox reactivity of transition metal centers can be augmented by nearby redox-active inorganic or organic moieties. In some cases, these functional groups can even allow a metal center to participate in reactions that were previously inaccessible to both the metal center and the functional group by themselves. Our research groups have been synthesizing and characterizing coordination complexes with polydentate quinol-containing ligands. Quinol is capable of being reversibly oxidized by either one or two electrons to semiquinone or para-quinone, respectively. Functionally, quinol behaves much differently than phenol, even though the pKa values of the first O-H bonds are nearly identical.The redox activity of the quinol in the polydentate ligand can augment the abilities of bound redox-active metals to catalyze the dismutation of O2-• and H2O2. These complexes can thereby act as high-performing functional mimics of superoxide dismutase (SOD) and catalase (CAT) enzymes, which exclusively use redox-active metals to transfer electrons to and from these reactive oxygen species (ROS). The quinols augment the activity of redox-active metals by stabilizing higher-valent metal species, providing alternative redox partners for the oxidation and reduction of reactive oxygen species, and protecting the catalyst from destructive side reactions. The covalently attached quinols can even enable redox-inactive Zn(II) to catalyze the degradation of ROS. With the Zn(II)-containing SOD and CAT mimics, the organic redox couple entirely substitutes for the inorganic redox couples used by the enzymes. The ligand structure modulates the antioxidant activity, and thus far, we have found that compounds that have poor or negligible SOD activity can nonetheless behave as efficient CAT mimics.Quinol-containing ligands have also been used to prepare electrocatalysts for dioxygen reduction, functionally mimicking the enzyme cytochrome c oxidase. The installation of quinols can boost electrocatalytic activity and even enable otherwise inactive ligand frameworks to support electrocatalysis. The quinols can also shift the product selectivity of O2 reduction from H2O2 to H2O without markedly increasing the effective overpotential. Distinct control of the coordination environment around the metal center allows the most successful of these catalysts to use economic and naturally abundant first-row transition metals such as iron and cobalt to selectively reduce O2 to H2O at low effective overpotentials. With iron, we have found that the electrocatalysts can enter the catalytic cycle as either an Fe(II) or Fe(III) species with no difference in turnover frequency. The entry point to the cycle, however, has a marked impact on the effective overpotential, with the Fe(III) species thus far being more efficient.

Miniaturize the Redox Flow Battery for Accelerated Materials Discovery and Development

Abstract Redox flow batteries are a promising technology for grid-scale energy storage. The aqueous organic redox flow battery is of particular interest for its potentially low material cost and sustainability. Developing novel organic active material for flow battery electrolytes typically entails molecular engineering toward desired properties, necessitating organic synthesis. In a research laboratory setting, the synthesis of specifically designed organic molecules featuring targeted functional groups is time and resources intensive. In the past, synthesizing materials required for battery testing has often required gram-scale production, presenting considerable constraints on the pace of novel organic material discovery. In this report, we introduce a miniaturized cell design that mandates only milligram-scale material synthesis while yielding testing outcomes equivalent or superior to those reported with other commercially available or homemade flow cells in the literature. The test results under various pH conditions validate the scale-down strategy to accelerate the flow battery material discovery and development using the newly designed mini cell. This approach offers researchers an efficient means to notably reduce the time and resource required to develop novel materials for flow batteries.

Flow field design and visualization for flow-through type aqueous organic redox flow batteries

Aqueous organic redox flow batteries (AORFBs), which exploit the reversible redox reactions of water-soluble organic electrolytes to store electricity, have emerged as a promising electrochemical energy storage technology. Organic electrolytes possess fast electron-transfer rates that are two or three orders of magnitude faster than those of their inorganic or organometallic counterparts; therefore, their performance at the electrode is limited by mass transport. Direct adoption of conventional cell stacks with flow fields designed for inorganic electrolytes may compromise AORFB performance owing to severe cell polarization. Here, we report the design of a flow field for flow-through type AORFBs based on three-dimensional multiphysics simulation, to realize the uniform distribution of electrolyte flow and flow enhancements within a porous electrode. The electrolyte flow is visualized by operando imaging. Our results show that multistep distributive flow channels at the inlet and point-contact blocks at the outlet are crucial geometrical merits of the flow field, significantly reducing local concentration overpotentials. The prototype pH-neutral TEMPTMA/MV cell at 1.5 M assembled with the optimized flow field exhibits a peak power density of 267.3 mW cm-2. The flow field design enables charging of the cell at current densities up to 300 mA cm-2, which is unachievable with the conventional serpentine flow field, where immediate voltage cutoff of the cell occurs. Our results highlight the importance of AORFB cell stack engineering and provide a method to visualize electrolyte flow, which will be appealing to the field of aqueous flow batteries.

Manipulating Aggregate Electrochemistry for High‐Performance Organic Redox Flow Batteries

Organic molecule in solutions is the energy storage unit in the organic redox flow batteries (ORFBs), of which the aggregation is acknowledged pivotal but has been rarely investigated. By establishing a pyridinium library, the manipulation over the aggregation in solutions is investigated at the molecular level. Both theoretical calculations and physiochemical methods are used to characterize the aggregate’s structure, and salient findings are as follows. First, the singly‐reduced monoradicals simultaneously aggregate in a concentrated solution, which is driven by the solvation effect, orbital overlap and dispersion interaction. Second, the aggregation can be manipulated by the molecular engineering strategy and counteracted by introducing either electrostatic repulsive force or twisted geometry. Third, the monoradical’s aggregation yields a decrease in the molecular singly occupied molecular orbital energy level and a linear scaling relationship with its thermodynamic potential. As a result, the increase in the concentration lowers the battery’s voltage, which counteracts its effort to increase the battery’s energy density. The anti‐aggregation is proven effective in breaking the scaling relationship and accordingly, a molecular strategy to manipulate aggregate electrochemistry is developed. This work provides physical insights into the electrolytic solution and chemical strategy for optimizing the flow battery.

Organic redox flow batteries in non-aqueous electrolyte solutions.

Redox flow batteries (RFBs) are gaining significant attention due to the growing demand for sustainable energy storage solutions. In contrast to conventional aqueous vanadium RFBs, which have a restricted voltage range resulting from the use of water and vanadium, the utilization of redox-active organic molecules (ROMs) as active materials broadens the range of applicable liquid media to include non-aqueous electrolyte solutions. The extended voltage range of non-aqueous media, exceeding 2 V, facilitates the establishment of high-energy storage systems. Additionally, considering the higher cost of non-aqueous solvents compared to water, the objective in developing non-aqueous electrolyte solution-based organic RFBs (NRFBs) is to efficiently install these systems in a compact manner and explore unique applications distinct from those associated with aqueous RFBs, which are typically deployed for grid-scale energy storage systems. This review presents recent research progress in ROMs, electrolytes, and membranes in NRFBs. Furthermore, we address the prevailing challenges that require revolution, encompassing a narrow cell voltage range, insufficient solubility, chemical instability, and the crossover of ROMs. Through this exploration, the review contributes to the understanding of the current landscape and potential advancements in NRFB technology and encourages researchers and professionals in the energy field to explore this emerging technology as a potential solution to global environmental challenges.

Incorporating MXene with Redox Carriers on Capacitive Carbon Cloth-Based Freestanding Electrodes for Power Applications

Abstract Battery-like organic materials including quinone-based electrodes with electrochemical activity have been extensively investigated for their use as electrode materials in energy storage devices due to their economic competitiveness and sustainable benefits. However, the intrinsic electrical insulating nature of organic quinones and their electrochemical reactivity limit power capability and stability upon charge/discharge cycling, respectively. Here, we report the preparation of a concentric layered architecture, MXene/Anthraquinone/Carbon Cloth (M/AQ/CC), by physisorption of anthraquinone onto the surface of carbon cloth via non-covalent π–π interactions, followed by dipping in exfoliated MXene suspension. The M/AQ/CC electrode, with a high mass loading (18.2 mg cm-2), delivered a capacity of 46 mAh g-1 (about 1 mAh cm-2 areal capacity or 6 mAh mL-1 volume) at 0.5 A g-1, with good rate performance and an enhanced cyclability over 5k cycles. This simple preparation method can also be applied to incorporate MXene with a series of alternative organic redox carriers on freestanding carbon cloth, including thionin acetate and anthraquinone-2-sulfonate. The improvement in electrochemical performance highlights an efficient approach to store more charges via redox reactions from organic quinones pi-stacked at carbon surfaces, thanks to a protective MXene shield that stabilizes the Faradaic behavior of quinones over repetitive charge-discharge processes. The simplicity and versatility of this method should enable design of many advanced electrode materials based on MXene/quinones/carbon cloth for power devices

Close‐Packed One‐Dimensional Coordination Polymer Cathode with Fast Kinetics for Sodium‐Ion Batteries

AbstractSustainable sodium‐ion batteries (SIBs) have gained tremendous attention; however, the large‐sized Na+ poses serious challenges on the development of inorganic‐based cathodes. To overcome the issues, metal–organic electrode materials are appealing because they combine attractive characteristics of organic redox centers (e. g., flexibility, highly reversible redox properties, fast kinetics (regardless of size and charge of guest ions), structural/redox tunability, and resource abundance) with structural stability arising from metal‐ligand coordination. Herein, a one‐dimensional copper−benzoquinoid coordination polymer (CP), [CuL(Py)2]n, (LH4=1,4‐dicyano‐2,3,5,6‐tetrahydroxybenzene, Py=pyridine) is investigated as cathode for SIBs. As opposed to most CPs reported for SIBs which possess high porosity and surface area, this close‐packed CP can deliver discharge capacity as high as 277 mAh g−1 at 2C (~523 mA g−1), and at extremely high rates of 50C and 300C (~13 and 78 A g−1), reversible capacities of 131 and 74 mAh g−1 still can be delivered, respectively. The transport kinetics of Na+ in [CuL(Py)2]n is found to be even faster than that of Li+ despite the close‐packed structure. The mechanistic and kinetic studies have been performed. The findings gained in this work undoubtedly unravel a potential design strategy for high‐performance metal–organic electrode materials for emerging post‐Li‐ion batteries.

Redox Polymers: Opportunities and Challenges in their Unique Functionalities

AbstractThe growing demand for energy‐storage devices has raised inevitable concerns regarding the availability of redox‐active inorganic compounds and metals. It is expected that some of the inorganic compounds will be replaced by organic redox polymers, which are produced from abundant sources using environmentally benign processes, and they exhibit inherent advantages, including flexibility, processability, and biocompatibility. Redox polymers contain groups that can be reversibly reduced and oxidized by gaining and releasing electrons, respectively, and constitute an emerging class of functional organic materials. This article begins with a retrospective discussion of polymers and their electron exchange concepts, presenting them as old but new materials. The basics of electrochemical redox couples are briefly reintroduced, and the chemical design strategies for extending them to redox polymers are summarized. Subsequently, the efficient and reversible charge propagation and storage in densely populated redox‐active sites on soft polymer platforms are discussed. The potential to employ redox polymers in rechargeable charge‐storage applications and next‐generation devices is discussed, along with the current challenges and prospects. This outlook suggests fundamental questions and proposes interesting topics for redox polymers to facilitate their development as valuable materials for use in sustainable technologies.

A highly water-soluble phenoxazine quaternary ammonium compound catholyte for pH-neutral aqueous organic redox flow batteries

The pH-neutral aqueous redox flow battery (ARFB) is one of the most attractive flow batteries due to its non-corrosiveness, low-cost, and wider electrochemical stability window compared to those with acidic or alkaline electrolytes. However, there are few families of organic redox-active molecules available as catholyte materials for pH-neutral ARFBs. Herein, through incorporation of quaternary ammonium moiety into the redox-active phenoxazine nucleus, an organic catholyte material, N, N, N-trimethyl-2-(10H-phenoxazin-10-yl) ethan-1-aminium chloride (NEt-POZ) is achieved for pH-neutral ARFBs. The NEt-POZ has a high redox potential of 0.79 V versus SHE and rapid redox kinetics (0.23 cm s−1) as well as high water-solubility (∼2.6 M in H2O). Paired with a methyl viologen (MV) anolyte in the pH-neutral aqueous electrolyte, a viologen-phenoxazine ARFB full cell is assembled, which shows an open circuit voltage of ∼1.23 V. However, the results of long-term cycling experiments indicate low Coulomb efficiency and rapid declining capacity of the NEt-POZ catholyte. The mechanism analysis unveils that the unstable doubly oxidized tri-cations (NEt-POZ3+) formed via the disproportionation of radical di-cations (NEt-POZ2+) in solution readily react with chloride anions to form poly-chlorinated derivatives, which precipitate from the catholyte due to their poor water solubility, leading to a rapid decrease in capacity. When there is no chloride present in the electrolyte solution, highly reactive NEt-POZ3+ cations can interact with other counter-anions (such as sulfate and carbonate ions) and even water to form complex adducts.

Meta-substituted thienoviologen with enhanced radical stability via π-π interaction modulation for neutral aqueous organic flow batteries

The aqueous organic redox flow batteries (AORFBs) are recognized as the most promising large-scale storage technology for long-duration energy storage (LDES). Although viologen derivatives are widely used as anolyte materials for AORFBs, their practical application is strongly limited by weak conjugation and unstable radicals. Here, we present a novel thienoviologen derivative, [(NPr)2SV]Cl4, achieved utilizing a meta-substitution approach based on the pristine viologen derivatives ( [(NPr)2V]Cl4). Compared to other ortho- and para-substitution methods, this strategy features a locked plane configuration (0.14°), effectively regulating π-π interactions and suppressing reactivity between radical and oxygen, which is confirmed via X-ray single-crystal structural analyses, spectroscopy techniques, molecular dynamics simulation accompanied by linear ion trap mass spectrometry experiments. Additionally, the meta-substituted [(NPr)2SV]Cl4 significantly improves water solubility (2.39 M), enhances aromaticity, and extends radical lifetime compared with para-substituted [(NPr)2TV]Cl4. Consequently, the cycling stability of the [(NPr)2SV]Cl4-based AORFB over 2500 cycles is 4.1 times higher than that of [(NPr)2TV]Cl4. Furthermore, the 0.5 M battery delivers an impressive 99.83% capacity retention during 200 cycles and a power density of 147 mW cm-2.

Nanocellulose-based ion-selective membranes for an aqueous organic redox flow battery

Nanocellulose-based ion-selective membranes for an aqueous organic redox flow battery

Metal Coordination Compounds for Organic Redox Flow Batteries

AbstractAlong with the continuous optimization of the energy structure, more and more electricity come from intermittent renewable energy sources such as wind and solar energy. Redox flow batteries (RFBs) have the advantage that energy and power can be regulated independently, so they are widely used in large‐scale energy storage. Redox active materials are the important components of RFBs, which determine the performance of the battery and the cost of energy storage. Some metal coordination compounds (MCCs) and their derivatives have been considered redox active materials that can replace metal‐based redox flow batteries due to their properties such as tunability, high abundance and sustainability. MCCs can provide higher energy density because they are highly soluble both in the initial state and in any charged state during the battery cycling process. MCCs have also attracted a lot of attention from researchers because of their high economic value, low toxicity, and wide availability. This review provides an overview of the recent development of soluble metal coordination compounds, such as Ferrocene, and concludes with an in‐depth discussion of the prospects of metal coordination compounds for application in organic redox flow batteries.

Boosting Thermogalvanic Cell Performance through Synergistic Redox and Thermogalvanic Corrosion.

Thermogalvanic cells with organic redox couple (OTGCs) have received significant attention for low-grade heat harvesting due to their high thermopower, versatile molecular design, and tailorable physiochemical properties. However, their thermogalvanic conversion power output is largely hindered by slow kinetic rate, which limits practical applications. In this work, we demonstrate a high-performance liquid quinone/hydroquinone (Q/HQ) based OTGC by synergistic coupling redox reaction and thermogalvanic corrosion. By adding hydrochloric acid (HCl) into electrolyte solution, HCl not only boosts intrinsic redox kinetic rate of Q/HQ, but also induces rapid thermogalvanic corrosion of the copper electrode. Notably, these two processes reinforce each other kinetically. Consequently, the Q/HQ-based OTGC exhibits a rapid kinetic rate alongside an increased thermopower, leading to a significantly enhanced power output density. As a result, the Q/HQ-based OTGC achieves an enhanced effective electrical conductivity σeff of 4.22 S m-1 and a record high normalized power density Pmax (ΔT)-2 of 108.7 μW m-2 K-2. This strategy provides a feasible and effective method for development of high-performance OTGCs.

A Multielectron and High-Potential Spirobifluorene-Based Posolyte for Aqueous Redox Flow Batteries.

The rising energy demand driven by human activity has posed pressing challenges in embracing renewable energy, necessitating advances in energy storage technologies to maximize their utilization efficiency. Recent studies in aqueous organic redox flow batteries have focused primarily on the development of organic negative electrolytes, while the progress in organic positive electrolytes remains constrained by limitations in their redox potentials and effective electron concentrations. Herein, we report a spatially twisted chlorinated spirobifluorene ammonium salts (CSFAs), created through an unexpected green chlorination-protection pathway during the initial cycling in the flow battery cell, utilizing chloride ions from counterions in aqueous solution. The chlorinated, nonplanar spiral structure of CSFAs possesses a one-step four-electron transfer electrochemical property and offers exceptional resistance to nucleophilic attacks, exhibiting an unprecedented redox potential as high as 1.05 V (vs. SHE). A full redox flow battery based on CSFA-Cl (chloride ions as the counter ions) with 1.4 M electron concentration achieved an average coulombic efficiency exceeding 99.4 % and a capacity utilization reaching 95 % of the four-electron capacity for a stable cycling over 250 cycles (~22 days). The present work exemplifies the use of side reactions to develop new redox species, which can be extended to create more structurally versatile energy storage materials.

Exploring Pyrazine-Based Organic Redox Couples for Enhanced Thermoelectric Performance in Wearable Energy Harvesters.

Thermoelectric generators (TEGs) based on thermogalvanic cells can convert low-temperature waste heat into electricity. Organic redox couples are well-suited for wearable devices due to their nontoxicity and the potential to enhance the ionic Seebeck coefficient through functional-group modifications. Pyrazine-based organic redox couples with different functional groups is comparatively analyzed through cyclic voltammetry under varying temperatures.The results reveal substantial differences in entropy changes with temperature and highlight 2,5-pyrazinedicarboxylic acid dihydrate (PDCA) as the optimal candidate.How the functional groups of the pyrazine compounds impact the ionic Seebeck coefficient is examined, by calculating the electrostatic potential based on density functional theory.To evaluate the thermoelectric properties, PDCA is integrated in different concentrations into a double-network hydrogel comprising poly(vinyl alcohol) and polyacrylamide. The resulting champion device exhibits an impressive ionic Seebeck coefficient (Si) of 2.99mV K-1, with ionic and thermal conductivities of ≈67.6 µS cm-1 and ≈0.49W m-1 K-1, respectively.Finally, a TEG is constructed by connecting 36 pieces of 20× 10-3 m PDCA-soaked hydrogel in series. It achieves a maximum power output of ≈0.28 µW under a temperature gradient of 28.3 °C and can power a small light-emitting diode. These findings highlight the significant potential of TEGs for wearable devices.

Alizarin Based Metal Organic Redox Flow Battery as an Efficient Storage Device for Renewable Energy Sources

Redox Flow Battery (RFB) technology is the most attractive energy storage system for storing renewable energy sources in the form of electrical energy that can be fed into power networks. However, there are many challenges associated with RFB technology in terms of cost, low energy density, and scarcity of active materials. To address these issues, herein we report an innovative Metal-Organic Redox Flow Battery (MORFB) technology involving manganese ions as catholyte and alizarin red S (ARS), an anthraquinone derivatives as anolyte. The newly designed Mn/ARS redox flow cell exhibits the open circuit voltage of 1.432 V vs Ag/AgCl and possessing reasonably good cycling performance with 99.9% capacity retention even after 100 cycles.

Mechanistic Analysis of Lithium-Air Battery with Organic Redox Mediator-Coated Air-Electrode

Redox mediators (RMs) suppress the charging overpotential to enhance the cycle performance of lithium-air batteries (LABs), but inappropriate RM incorporation can adversely shorten cycle life. In this study, three typical organic RMs; tetrathiafulvalene (TTF), 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO), and 10-methylphenothiazine (MPT), were incorporated into the air-electrode (AE) of the LAB (RM-on-AE), rather than dissolving them in the electrolyte (RM-in-EL), to maximize the RM effect throughout the cycle life. The discharge/charge cycle test confirmed that the cells with RM-on-AE prevented the reductive decomposition of RM with the lithium anode, deriving the RM effect for a longer cycle life than the cells with RM-in-EL. The measurement of AE deposits revealed that the TTF- and TEMPO-on-AE cells failed to generate a quantitative amount of Li2O2 discharge product. In contrast, the MPT-on-AE provided a 96% yield of Li2O2 after the first discharge because of the reductive tolerance of the MPT as organic RM. The quantitative analysis also revealed an accumulation of Li2CO3 on the AEs, along with the generation of carboxylate, as the side products of irrelevant battery reactions. This study provides a practical methodology for selecting RMs and their incorporation for developing long-life LABs.

Sediment properties control riverine methane emissions: A case study of the Liao River in northern China

River and stream sediments act as biogeochemical reactors for greenhouse gases, particularly methane. However, understanding how riverbed sediment properties influence river carbon emissions remains relatively unclear. The Liao River in northern China is a typical watershed with heterogeneous water and sediment sources, characterized by varying sediment properties. In this study, we surveyed CH4 and CO2 emissions from its mainstem and tributaries during flood and dry seasons. We found consistent seasonal patterns in CH4 and CO2 emissions, with peaks occurring during the flood season. The average CH4 and CO2 fluxes were 1.64 ± 1.80 mmol·m−2·d−1 and 59.66 ± 44.60 mmol·m−2·d−1, respectively. Notably, the percentage of sediment silt was significantly correlated with CH4 concentration and flux (R2 = 0.12−0.30, p < 0.05). Fine particles dominated the availability of sediment organic matter and redox conditions, which were related to riverine CH4 production and emissions. Structural equation modeling revealed that both grain size and the percentage of TOC (total organic carbon) directly influenced riverine CH4 and CO2 emissions. The organic content and redox conditions of the riverbed sediment collectively explained 65% of riverine CH4 emissions, while grain size composition indirectly controlled CH4 emissions by altering sediment substrate quality and redox conditions. In contrast, river CO2 emissions were only weakly dependent on anaerobic metabolism in riverbed sediments. These findings enhance our understanding of the sources and metabolic mechanisms of riverine CH4 and CO2 emissions and offer potential improvements for estimating carbon fluxes in regional or global riverine networks by considering riverbed sediment properties.

Tuning Electron Transfer Coupling and Exchange Interaction in Bis-triarylamine Radical Cations and Dications by Bridge Electron Density.

The influence of the electron density of a bridge connecting two redox centers on both the intervalence hole transfer and the magnetic superexchange was investigated in a series of bridged bis-triarylamine mono- and dications. In this series, the bridge was 2,7-fluorenyl, where the bridge electron density was modified by substituents at the 9-position. For the mixed-valence monocations, the observation of both an intervalence charge transfer (IVCT) band and an absorption band associated with an electron transfer from the bridging fluorene to the triarylamine radical cation centers allowed determination of the electron transfer couplings in the framework of the three-state generalized Mulliken-Hush theory. Comparison of the derived couplings with those obtained from a classical two-state approach demonstrates an enhancement of the electronic coupling which increases with decreasing bridge state energy. For the dicationic diradical counterparts, the singlet-triplet gap (exchange interaction) was determined both experimentally and by quantum chemical methods. Hereby, an increase of antiferromagnetic coupling with a lowering of the bridge state energy by electron donating substituents was observed. Analysis of the involved molecular orbitals suggests that the ferromagnetic coupling is inversely proportional to the square of the bridge energy, which is also supported by the experimental findings. This influence of the bridge state energy on both types of interactions, electron transfer and magnetic exchange, provides a design guideline for fine-tuning the properties of electronically coupled organic redox dyads by variation of the bridge electron density.

Chemical Activation of S/Li2S in Li-S Batteries by a Bidirectional Organic Redox Mediator

Chemical Activation of S/Li2S in Li-S Batteries by a Bidirectional Organic Redox Mediator