Single-Molecule Confinement Induced Intrinsic Multi-Electron Redox-Activity to Enhance Supercapacitor Performance

Aggregation of polyoxometalates(POM)is largely responsible for the reduced performance of POM-based energy-storage systems.To address this challenge,here,the precise confinement of single Keggin-type POM molecule in a porous carbon(PC)of unimodal super-micropore(micro-PC)is realized.Such precise single-molecule confinement enables sufficient activity center exposure and maximum electron-transfer from micro-PC to POM,which well stabilizes the electron-accepting molecules and thoroughly activates its inherent multi-electron redox-activity.In particular,the redox-activities and electron-accepting properties of the confined POM molecule are revealed to be super-micropore pore size-dependent by experiment and spectroscopy as well as theoretical calculation.Meanwhile,the molecularly dispersed POM molecules confined steadily in the“cage”of micro-PC exhibit unprecedented large-negative-potential stability and multiple-peak redox-activity at an ultra-low loading of~11.4 wt%.As a result,the fabricated solid-state supercapacitor achieves a remarkable areal capacitance,ultrahigh energy and power density of 443 mF cm^(-2),0.12 mWh cm^(-2)and 21.1 mW cm^(-2),respectively.This work establishes a novel strategy for the precise confinement of single POM molecule,providing a versatile approach to inducing the intrinsic activity of POMs for advanced energy-storage systems.

Thermally Chargeable Proton Capacitor Based on Redox-Active Effect for Energy Storage and Low-Grade Heat Conversion

Thermal energy is abundantly available in our daily life and industrial production,and especially,low-grade heat is often regarded as a byproduct.Collecting and utilizing this ignored energy by low-cost and simple technologies may become a smart countermeasure to relieve the energy crisis.Here,a unique device has been demonstrated to achieve high value-added conversion of low-grade heat by introducing redox-active organic alizarin(AZ)onto N-doped hollow carbon nanofibers(N–HCNF)surface.As-prepared N–HCNF/AZ can deliver a high specific capacitance of 514.3 F g^(-1)(at 1 A g^(-1))and an outstanding rate capability of 60.3%even at 50 A g^(-1).Meanwhile,the assembled symmetric proton capacitor can deliver a high energy density of 28.0 Wh kg^(-1) at 350.0 W kg^(-1) and a maximum power density of 35.0 kW kg^(-1) at 17.0 Wh kg^(-1).Significantly,the thermally chargeable proton capacitors can attain a surprisingly high Seebeck coefficient of 15.3 mV K^(-1) and a power factor of 6.02µW g^(-1).Taking advantage of such high performance,a satisfying open-circuit voltage of 481.0 mV with a temperature difference of 54 K is achieved.This research provides new insights into construction of high value-added energy systems requiring high electrochemical performances.

Ag-integrated mixed metallic Co-Fe-Ni-Mn hydroxide composite as advanced electrode for high-performance hybrid supercapacitors

Direct growth of redox-active noble metals and rational design of multifunctional electrochemical active materials play crucial roles in developing novel electrode materials for energy storage devices.In this regard,silver(Ag)has attracted great attention in the design of efficient electrodes.Inspired by the house/building process,which means electing the right land,it lays a strong foundation and building essential columns for a complex structure.Herein,we report the construction of multifaceted heterostructure cobalt-iron hydroxide(CFOH)nanowires(NWs)@nickel cobalt manganese hydroxides and/or hydrate(NCMOH)nanosheets(NSs)on the Ag-deposited nickel foam and carbon cloth(i.e.,Ag/NF and Ag/CC)substrates.Moreover,the formation and charge storage mechanism of Ag are described,and these contribute to good conductive and redox chemistry features.The switching architectural integrity of metal and redox materials on metallic frames may significantly boost charge storage and rate performance with noticeable drop in resistance.The as-fabricated Ag@CFOH@NCMOH/NF electrode delivered superior areal capacity value of 2081.9μA h cm^(-2)at 5 mA cm^(-2).Moreover,as-assembled hybrid cell based on NF(HC/NF)device exhibited remarkable areal capacity value of 1.82 mA h cm^(-2)at 5 mA cm^(-2)with excellent rate capability of 74.77%even at 70 mA cm^(-2)Furthermore,HC/NF device achieved maximum energy and power densities of 1.39 mW h cm^(-2)and 42.35 mW cm^(-2),respectively.To verify practical applicability,both devices were also tested to serve as a self-charging station for various portable electronic devices.

Pairing nitroxyl radical and phenazine with electron-withdrawing/-donating substituents in “water-in-ionic liquid” for high-voltage aqueous redox flow batteries

Aqueous redox-active organic materials-base electrolytes are sustainable alternatives to vanadium-based electrolyte for redoxflow batteries(RFBs)due to the advantages of high ionic conductivity,environmentally benign,safety and low cost.However,the underexplored redox properties of organic materials and the narrow thermodynamic electrolysis window of water(1.23 V)hinder their wide applications.Therefore,seeking suitable organic redox couples and aqueous electrolytes with a high output voltage is highly suggested for advancing the aqueous organic RFBs.In this work,the functionalized phenazine and nitroxyl radical with electron-donating and electron-withdrawing group exhibit redox potential of-0.88 V and 0.78 V vs.Ag,respectively,in“water-in-ionic liquid”supporting electrolytes.Raman spectra reveal that the activity of water is largely suppressed in“water-in-ionic liquid”due to the enhanced hydrogen bond interactions between ionic liquid and water,enabling an electrochemical stability window above 3 V.“Water-in-ionic liquid”supporting electrolytes help to shift redox potential of nitroxyl radical and enable the redox activity of functionalized phenazine.The assembled aqueous RFB allows a theoretical cell voltage of 1.66 V and shows a practical discharge voltage of 1.5 V in the“water-in-ionic liquid”electrolytes.Meanwhile,capacity retention of 99.91%per cycle is achieved over 500 charge/discharge cycles.A power density of 112 mW cm^(-2) is obtained at a current density of 30 mA cm^(-2).This work highlights the importance of rationally combining supporting electrolytes and organic molecules to achieve high-voltage aqueous RFBs.

Antioxidant capacity and concentration of redox-active trace mineral in fully weaned intra-uterine growth retardation piglets

Background： The redox status of intra-uterine growth retardation（IUGR） piglets post-weaning has been poorly studied.Methods： Newborns from twenty-four sows were weighted, weaned at 21 d and fed a starter diet until sampling.Sampling was done at 14 d post-weaning. A piglet was defined as IUGR when its birth weight was 2 SD below the mean birth weight of the total population. At weaning, eighteen piglets with nearly equal body weight from each category（i.e. IUGR or normal birth weight（NBW） piglets） were selected and then allocated to two treatments,consisted of six replicates with each pen having three piglets.Results： Compared with NBW group, IUGR significantly decreased average daily gain（P 〈 0.001）, average daily feed intake（P = 0.003）, and feed efficiency（P 〈 0.001） of piglets during the first two weeks post-weaning. IUGR decreased the activities of total antioxidant capacity（P = 0.019）, total superoxide dismutase（T-SOD, P = 0.023）,and ceruloplasmin（P = 0.044） but increased the levels of malondialdehyde（P = 0.040） and protein carbonyl（P = 0.010） in plasma. Similarly, the decreased activities of T-SOD（P = 0.005）, copper- and zinc-containing superoxide dismutase（Cu/Zn-SOD, P = 0.002）, and catalase（P = 0.049） was observed in the liver of IUGR piglets than these of NBW piglets. IUGR decreased hepatic Cu/Zn-SOD activity（P = 0.023） per unit of Cu/Zn-SOD protein in piglets when compared with NBW piglets. In addition, IUGR piglets exhibited the decreases in accumulation of copper in both plasma（P = 0.001） and liver（P = 0.014）, as well as the concentrations of iron（P = 0.002） and zinc（P = 0.048） in liver. Compared with NBW, IUGR down-regulated m RNA expression of Cu/Zn-SOD（P = 0.021） in the liver of piglets.Conclusions： The results indicated that IUGR impaired antioxidant capacity and resulted in oxidative damage in fully weaned piglets, which might be associated with the decreased levels of redox-active trace minerals. This study highlights the importance of redox status in IUGR offspring and provides a rationale for alleviating oxidative damage by dietary interventions aiming to supplement trace minerals and to restore redox balance in the future.

Electrocatalytic hydrogen evolution from water at low overpotentials with cobalt complexes supported by redox-active bipyridyl-NHC donors

Three cobalt complexes bearing tunable,redox-active bipyridyl N-heterocyclic carbene(NHC)-based ligands have been studied for electrocatalytic hydrogen evolution from aqueous solutions.The effect of structural modifications to the ligand framework is investigated across the catalyst series,which includes a non-macrocyclic derivative(1-Co)and 16-(2-Co)and 15-(3-Co)membered macrocycles.A structure-activity relationship is demonstrated,in which the macrocyclic complexes have greater activity compared to their non-macrocyclic counterpart with the most rigid catalyst,supported by the 15-membered macrocycle,performing best overall.Indeed,3-Co catalyzes H2 evolution from aqueous pH 4 acetate buffer with a Faradaic efficiency of 97%at a low overpotential of 330 mV.Mechanistic studies are consistent with formation of a cobalt-hydride species that is subsequently protonated to evolve H2 via a heterolytic pathway.

Synergistic interaction between redox-active electrolytes and functionalized carbon in increasing the performance of electric double-layer capacitors

The increasing demand of high-performance supercapacitors has aroused great interest in developing specific capacitance and energy density. Active carbon （AC） has attracted much attention as a promising electrode material for electric double-layer capacitors （EDLCs）. Here, a facile strategy has been employed to fabricate high-performance EDLCs using the surface-oxygen functionalized active carbon （FAC） as an electrode and 2 M KOH with K3Fe（CN）6 as an electrolyte. In this system, K3Fe（CN）6 was used as a redox additive to enhance the performance of EDLCs. A 38.5% increase in specific capacitance （207.7 F g-1） was achieved compared with the KOH electrolyte without adding K3Fe（CN）G （152.9 F g-1）, due to the synergistic effects between oxygenic functional groups and redox electrolyte. These findings provide an alternative route to improve the performance of EDLCs, which are promising candidates for the broad applications of high-performance supercapacitors.

Fundamental Perspectives on the Electrochemical Water Applications of Metal-Organic Frameworks

Metal-organic frameworks(MOFs),a family of highly porous materials possessing huge surface areas and feasible chemical tunability,are emerging as critical functional materials to solve the growing challenges associated with energy-water systems,such as water scarcity issues.In this contribution,the roles of MOFs are highlighted in electrochemical-based water applications(i.e.,reactions,sensing,and separations),where MOF-based functional materials exhibit outstanding performances in detecting/removing pollutants,recovering resources,and harvesting energies from different water sources.Compared with the pristine MOFs,the efficiency and/or selectivity can be further enhanced via rational structural modulation of MOFs(e.g.,partial metal substitution)or integration of MOFs with other functional materials(e.g.,metal clusters and reduced graphene oxide).Several key factors/properties that affect the performances of MOF-based materials are also reviewed,including electronic structures,nanoconfined effects,stability,conductivity,and atomic structures.The advancement in the fundamental understanding of these key factors is expected to shed light on the functioning mechanisms of MOFs(e.g.,charge transfer pathways and guest-host interactions),which will subsequently accelerate the integration of precisely designed MOFs into electrochemical architectures to achieve highly effective water remediation with optimized selectivity and long-term stability.

A high-capacity viologen-based anolyte for high energy density neutral pH aqueous redox-flow batteries

Redox-flow batteries(RFBs)are a promising energy storage technology with remarkable scalability and safety for storing vast amounts of renewable energy and mitigating outputfluctuations of renewable power grids.We demonstrate a neutral pH aqueous RFB using a custom-designed 1’,1’’’,1’’’’’-(benzene-1,3,5-triyltris(methylene))tris(1-(3-(trimethyl ammonio)propyl)-[4’’,4’’’-bipyridine]-1,1’-diium)nonachloride(BTTMPB)as a 3 e-storage anolyte.The custom design with the high polarization in charge density has led to the excellent water solubility of 4.0 M in H_(2)O(321.6 A h L^(-1))and 2.4 M in 2.0 M NaCl(192.9 A h L^(-1)).The density functional theory(DFT)calculations and electrochemical experiments have shown 3 e-storage response of BTTMPB with a diffusion coefficient of 3.1×10^(-6)cm^(2) s^(-1)and rate con-stant of 1.6×10^(-2)cm s^(-1) for thefirst reduction process.The synthesized anolyte was paired with(Ferrocenylmethyl)trimethylammonium chloride(FcNCl)as catholyte enabling a 0.92 V aqueous RFB with 125.9 W h L^(-1)theoretical energy density.The aqueous RFB has an excellent cycling performance from 10-30 m A cm^(-2),energy efficiency up to 80%,capacity retention of 99.96%per cycle at 20 m A cm^(-2),and a high demonstrated energy density of 29.1 W h L^(-1).

Redox-Active Dihydrophenazine-Based Macrocycle:Synthesis,Conformation-Adaptive Behavior and Host-Guest Complexation with Tetracyanoquinodimethane

A novel macrocycle based on conformation-adaptive and electron-rich dihydrophenazine was designed and synthesized.On the one hand,the macrocycle showed host-guest interactions with tetracyanoquinodimethane(TCNQ)driving by charge transfer interaction between them.Meanwhile,host-guest complexation was accompanied by fluorescence quenching and conformational change of the macrocycle.On the other hand,the oxidation of the macrocycle resulted in its diradical cation analogue and induced the release of the guest molecule TCNQ,thereby accomplishing reversible binding dynamics.Therefore,this work wellillustrates the chemical and structural versatility of dihydrophenazine in the synthesis of macrocycles and their host-guest chemistry.

Isoreticular Regulation of Two-Dimensional Redox-Active Covalent Organic Framework Cathodes for Enhanced Lithium-Ion Storage

A challenge facing scientists is the rational synthesis of highly crystalline covalent organic frameworks(COFs),consisting of both n-type and p-type redox-active units,as cathodes for high-performance lithium-ion batteries(LIBs).Herein,we apply reticular chemistry to regulate a COF platform with the kgm topology via an in-situ postsynthetic oxidation strategy.We integrate both n-type and p-type redox-active units into a resulting COF skeleton—TPDA-DQTA-COF,and this COF-based cathode shows an enhanced performance for LIBs compared to the parent TPDA-DMTA-COF.On account of dual redox-active units for PF6−/Li+costorage,the TPDADQTA-COF cathode presents the highly reversible capacity of 308 mAh g−1 at 0.2 A g^(−1) and the high energy density of 800 Wh kg^(−1).The long-term cycling experiment reveals a capacity retention of 91%after 200 cycles at a low current density of 0.5 A g^(−1).The combined Fourier transform infrared and X-ray photoelectron spectroscopy experiments suggest that the in-situ electrochemical oxidation from the C-OH to the C=O group of COFs occurs during the charging process.We believe our study demonstrates that the atomic-level modification of functional groups in COF-based cathode materials has a significant impact on the macroscopic performance of lithium-ion storage,clearly illustrating the structure-property relationship.

Mussel‑Inspired Redox‑Active and Hydrophilic Conductive Polymer Nanoparticles for Adhesive Hydrogel Bioelectronics

Conductive polymers(CPs)are generally insoluble,and developing hydrophilic CPs is significant to broaden the applications of CPs.In this work,a mussel-inspired strategy was proposed to construct hydrophilic CP nanoparticles(CP NPs),while endowing the CP NPs with redox activity and biocompatibility.This is a universal strategy applicable for a series of CPs,including polyaniline,polypyrrole,and poly(3,4-ethylenedioxythiophene).The catechol/quinone contained sulfonated lignin(LS)was doped into various CPs to form CP/LS NPs with hydrophilicity,conductivity,and redox activity.These CP/LS NPs were used as versatile nanofillers to prepare the conductive hydrogels with long-term adhesiveness.The CP/LS NPs-incorporated hydrogels have a good conductivity because of the uniform distribution of the hydrophilic NPs in the hydrogel network,forming a well-connected electric path.The hydrogel exhibits long-term adhesiveness,which is attributed to the mussel-inspired dynamic redox balance of catechol/quinone groups on the CP/LS NPs.This conductive and adhesive hydrogel shows good electroactivity and biocompatibility and therefore has broad applications in electrostimulation of tissue regeneration and implantable bioelectronics.

Opportunities and challenges of organic flow battery for electrochemical energy storage technology

For flow batteries(FBs), the current technologies are still expensive and have relatively low energy density, which limits their large-scale applications. Organic FBs(OFBs) which employ organic molecules as redox-active materials have been considered as one of the promising technologies for achieving lowcost and high-performance. Herein, we present a critical overview of the progress on the OFBs, including the design principles of key components(redox-active molecules, membranes, and electrodes) and the latest achievement in both aqueous and nonaqueous systems. Finally, future directions in explorations of the high-performance OFB for electrochemical energy storage are also highlighted.

Weak Intermolecular Interactions for Strengthening Organic Batteries

Organic batteries have attracted a lot of attention due to the advantages of flexibility,light weight,vast resources,low cost,recyclability,and ease to be functionalized through molecular design.The biggest difference between organic materials and inorganic materials is the relatively weak intermolecular interactions in organic materials but strong covalent or ionic bonds in inorganic materials,which is the inherent reason of their different physiochemical and electrochemical characteristics.Therefore,the relatively weak intermolecular interactions can indisputably affect the electrochemical performance of organic batteries significantly.Herein,the intermolecular interactions that are closely related to organic redox-active materials and unique in organic batteries are summarized into three parts:1)between neighbor active molecules,2)between active molecules and the conduction additives,and 3)between active molecules and the binders.We hope this short review can give a distinct viewpoint for better understanding the internal reasons of high-performance batteries and stimulate the deep studies of relatively weak intermolecular interactions for strengthening the performance of organic batteries.

Buffer anion effects on water oxidation catalysis: The case of Cu(Ⅲ) complex

Water oxidation is the bottleneck of artificial photosynthesis.Since the first ruthenium-based molecular water oxidation catalyst,the blue dimer,was reported by Meyer’ s group in 1982,catalysts based on transition metals have been widely employed to explore the mechanism of water oxidation.Because the oxidation of water requires harsh oxidative conditions,the stability of transition complexes under the relevant catalytic conditions has always been a challenge.In this work,we report the redox properties of a CuⅢ complex(TAML-CuⅢ] with a redox-active macrocyclic ligand(TAML) and its reactivity toward catalytic water oxidation.TAML-CuⅢ displayed a completely different electrochemical behavior from that of the TAML-CoⅢ complex previously reported by our group.TAML-CuⅢ can only be oxidized by one-electron oxidation of the ligand to form TAML·+-CuⅢand cannot achieve water activation through the ligand-centered proton-coupled electron transfer that takes place in the case of TAML-CoⅢ.The generated TAML·+-CuⅢ intermediate can undergo further oxidation and ligand hydrolysis with the assistance of borate anions,triggering the formation of a heterogeneous B/CuOx nanocatalyst Therefore,the choice of the buffer solution has a significant influence on the electrochemical behavior and stability of molecular water oxidation catalysts.

Development of organic redox-active materials in aqueous flow batteries: Current strategies and future perspectives

Aqueous redox flow batteries,by using redox-active molecules dissolved in nonflammable water solutions as electrolytes,are a promising technology for grid-scale energy storage.Organic redox-active materials offer a new opportunity for the construction of advanced flow batteries due to their advantages of potentially low cost,extensive structural diversity,tunable electrochemical properties,and high natural abundance.In this review,we present the emergence and development of organic redox-active materials for aqueous organic redox flow batteries(AORFBs),in particular,molecular engineering concepts and strategies of organic redox-active molecules.The typical design strategies based on organic redox species for high-capacity,high-stability,and high-voltage AORFBs are outlined and discussed.Molecular engineering of organic redox-active molecules for high aqueous solubility,high chemical/electrochemical stability,and multiple electron numbers as well as satisfactory redox potential gap between the redox pair is essential to realizing high-performance AORFBs.Beyond molecular engineering,the redoxtargeting strategy is an effective way to obtain high-capacity AORFBs.We further discuss and analyze the redox reaction mechanisms of organic redox species based on a series of electrochemical and spectroscopic approaches,and succinctly summarize the capacity degradation mechanisms of AORFBs.Furthermore,the current challenges,opportunities,and future directions of organic redox-active materials for AORFBs are presented in detail.

Redox-active humics support interspecies syntrophy and shift microbial community

The network of microbial electron transfer can establish a syntrophic association of microbes by connecting interspecies metabolisms, and a variety of redox-active shuttles in environment have been proved to accelerate the electron flow in a microbial community. Using humic substances as models, we investigated how different redox-active shuttles with different electrochemical properties influence interspecies electron transfer, and affect the shift of microbial communities. The co-culture of two species was constructed with supplements of humics, and the electron transfer between these two strains was found to be linked by humic acid with a wider window of redox potential and multi-peaks of redox reactions. Based on the shift of microbial composition, the humic substances with a wide potential window and multi-peaks of redox reactions for accepting and donating electrons could increase the biodiversity(Chao 1 and phylogenetic diversity) with a large extent. The mechanism by which redox-active shuttles mediate the microbial electron transfer network could facilitate our understanding of syntrophic interactions between microbes.

Application of a novel redox-active electrolyte in MnO_2-based supercapacitors

This paper reports a novel strategy for preparing redox-active electrolyte through introducing a redox-mediator(p-phenylenediamine,PPD) into KOH electrolyte for the application of ball-milled MnO 2-based supercapacitors.The morphology and compositions of ball-milled MnO 2 were characterized using scanning electron microscopy(SEM) and X-ray diffraction(XRD).The electrochemical properties of the supercapacitor were evaluated by cyclic voltammetry(CV),galvanostatic charge-discharge(GCD),and electrochemical impedance spectroscopy(EIS) techniques.The introduction of p-phenylenediamine significantly improves the performance of the supercapacitor.The electrode specific capacitance of the supercapacitor is 325.24 F g-1,increased by 6.25 folds compared with that of the unmodified system(44.87 F g-1) at the same current density,and the energy density has nearly a 10-fold increase,reaching 10.12 Wh Kg-1.In addition,the supercapacitor exhibits good cycle-life stability.

Redox-active nanoparticles for inflammatory bowel disease

Homeostasis of gut microbiota is extremely essential for maintaining nutrient metabolism and regulating immunological function.The increasing evidence suggests that inflammatory bowel disease(IBD)is strongly associated with dysregulation of gut microbiota.During activated inflammation,excessive reactive oxygen species(ROS)and reactive nitrogen species(RNS)produced by inflammatory cells play a detrimental role in regulating IBD and gut microbiota.ROS/RNS cause damage to the surrounding tissues,including nutrient absorption disorders,intestinal dysmotility and barrier dysfunction.Meanwhile,ROS/RNS provide terminal electron receptors for anaerobic respiration and support the bloom of facultative anaerobes,eventually causing gut microbiota dysbiosis.Redox-active nanoparticles(NPs)with catalytic properties or enzyme-like activities can effectively scavenge ROS/RNS,and selectively target inflamed sites via ultrasmall size-mediated enhanced permeation and retention(EPR)effect,showing great potential to regulate IBD and maintain the homeostasis of gut microbiota.In addition,the widespread application of NPs in commercial products 1 has increased their accumulation in healthy organisms,and the biological effects on normal microbiota resulting from long-term exposure of NPs to gastrointestinal tract also need attention.

Functionalizing MOF with Redox-Active Tetrazine Moiety for Improving the Performance as Cathode of Li-O_(2)Batteries

A redox-active tetrazine moiety is immobilized within a metal-organic framework(MOF)aiming at targeted construction of a cathode with improved performance for lithium–oxygen batteries.A 1,2,4,5-tetrazine(Tz)functionalized ligand is used to construct a nanoporous MOF,Tz-Mg-MOF-74,in which the redox activity of the Tz moiety is retained.Combining the redox activity of Tz with the porous nature of a MOF produced a Tz-Mg-MOF-74-based cathode with significantly improved electrochemical performance.Specifically,the material has improved sustainable capacity with a lower overpotential compared with otherwise similar batteries without Tz and other reported MOF-based catalysts.The present approach productively integrates electrochemical activity derived from redox-active moieties and MOFs,and this combination opens a new avenue for the design of effective materials for energy storage and conversion.