Herein,3‑aminopropyltriethoxysilane(APTES)was used to modify F‑containing silica slag(SS)by simple grafting and served as a multifunctional barrier layer.The amino group(—NH2)in the amino‑modified SS(NH2‑SS)forms lig...Herein,3‑aminopropyltriethoxysilane(APTES)was used to modify F‑containing silica slag(SS)by simple grafting and served as a multifunctional barrier layer.The amino group(—NH2)in the amino‑modified SS(NH2‑SS)forms ligand bonds or hydrogen bonds with sulfur ions in lithium polysulfides(LiPSs),thus inhibiting the shuttle effect.Electrochemical analyses demonstrated that lithium‑sulfur(Li‑S)batteries employing the NH2‑SS interlayer exhibited discharge specific capacities of 1048 and 789 mAh·g^(-1) at 0.2C and 2C,respectively,and even at 4C,the initial discharge specific capacity remained at 590 mAh·g^(-1),outperforming the Li‑S battery with unmodified SS as the interlayer.展开更多
Pb-Sn mixed perovskite solar cells(PSCs)are crucial components for realizing efficient all-perovskite tandem devices.However,their efficiency and stability are severely limited by oxidative degradation(Sn^(4+)formatio...Pb-Sn mixed perovskite solar cells(PSCs)are crucial components for realizing efficient all-perovskite tandem devices.However,their efficiency and stability are severely limited by oxidative degradation(Sn^(4+)formation)and metallic defects(Sn^(0)/Pb^(0)).In addition,the rapid and uncontrolled Sn^(2+)nucleation kinetics result in nonuniform crystallization.Herein,we introduce a natural redox shuttle glutathione(GSH)in Pb-Sn mixed PSCs,achieving regenerable antioxidation and crystallization regulation simultaneously.The reversible redox reactions between GSH and glutathione disulfide(GSSG)enable the self-healing of Sn^(4+)and Sn^(0)/Pb^(0)impurities,creating a regenerable antioxidation protective shell at the perovskite interfaces.Meanwhile,the strong coordination between GSH and perovskite regulates the crystallization process,optimizing the nucleation and crystallization kinetics.Furthermore,the GSH incorporation creates a high-quality charge separation junction at the perovskite/hole transport layer,facilitating carrier separation and extraction.The optimized Pb-Sn PSCs exhibit impressive power conversion efficiencies(PCEs)of up to 23.71%.The champion all-perovskite tandem PSCs with GSH achieve a PCE of 28.49%and retain 90%of the initial PCE after 560 h of continuous illumination.This work establishes a new nature-inspired redox shuttling strategy and elucidates its working mechanism,advancing the development of efficient and stable all-perovskite tandem solar cells.展开更多
Rechargeable alkali metal-sulfur(M-S)batteries,including Li/Na/K-S chemistries,have the potential to utilize abundant and low-cost sulfur cathodes yet offer high theoretical energy densities.However,their practical el...Rechargeable alkali metal-sulfur(M-S)batteries,including Li/Na/K-S chemistries,have the potential to utilize abundant and low-cost sulfur cathodes yet offer high theoretical energy densities.However,their practical electrochemical performance is fundamentally limited by the polysulfide shuttle effect.This challenge is particularly exacerbated in Na-S and K-S systems owing to larger metal-ion radii,weaker solvation energies,slower redox kinetics,and greater electrolyte-electrode incompatibilities compared to Li-S batteries.This review presents a comparative analysis of interface engineering strategies designed to suppress the shuttle effect across these three systems.Following a summary of sulfur cathode properties and reaction mechanisms,we systematically examine the origins of polysulfide shuttling.Our analysis progresses from functional separator design and interlayer enhancements to the implementation of solid-state electrolytes for root-cause inhibition.By evaluating interface engineering research specific to Na-S and K-S batteries,we elucidate both shared principles and unique challenges inherent to alkali M-S systems.Finally,we propose multifaceted solutions to achieve shuttlefree operation and enhance overall battery performance,thereby establishing a foundation for future advancements.展开更多
Zn-I_(2) batteries have emerged as promising next-generation energy storage systems owing to their inherent safety,environmental compatibility,rapid reaction kinetics,and small voltage hysteresis.Nevertheless,two crit...Zn-I_(2) batteries have emerged as promising next-generation energy storage systems owing to their inherent safety,environmental compatibility,rapid reaction kinetics,and small voltage hysteresis.Nevertheless,two critical challenges,i.e.,zinc dendrite growth and polyiodide shuttle effect,severely impede their commercial viability.To conquer these limitations,this study develops a multifunctional separator fabricated from straw-derived carboxylated nanocellulose,with its negative charge density further reinforced by anionic polyacrylamide incorporation.This modification simultaneously improves the separator’s mechanical properties,ionic conductivity,and Zn^(2+)ion transfer number.Remarkably,despite its ultrathin 20μm profile,the engineered separator demonstrates exceptional dendrite suppression and parasitic reaction inhibition,enabling Zn//Zn symmetric cells to achieve impressive cycle life(>1800 h at 2 m A cm^(-2)/2 m Ah cm^(-2))while maintaining robust performance even at ultrahigh areal capacities(25 m Ah cm^(-2)).Additionally,the separator’s anionic characteristic effectively blocks polyiodide migration through electrostatic repulsion,yielding Zn-I_(2) batteries with outstanding rate capability(120.7 m Ah g^(-1)at 5 A g^(-1))and excellent cyclability(94.2%capacity retention after 10,000 cycles).And superior cycling stability can still be achieved under zinc-deficient condition and pouch cell configuration.This work establishes a new paradigm for designing high-performance zinc-based energy storage systems through rational separator engineering.展开更多
Fe reducing bacteria(FRB),through extracellular electron transfer(EET)pathway,can reduce Fe(III)nanoparticles,thereby affecting the migration,transformation,and degradation of pollutants.However,the interaction of Fe(...Fe reducing bacteria(FRB),through extracellular electron transfer(EET)pathway,can reduce Fe(III)nanoparticles,thereby affecting the migration,transformation,and degradation of pollutants.However,the interaction of Fe(III)nanoparticles with the most commonly identified FRB,Geobacter sulfurreducens PCA,remains poorly understood.Herein,we demonstrated that the synergistic role of outer membrane proteins and periplasmic proteins in the EET process for-Fe_(2)O_(3),Fe3O4,and𝛽α-FeOOH nanoparticles by construction of multiple gene knockout strain.oxpG(involved in the type II secretion system)and omcST(outer membrane c-type cytochrome)medi-ated pathways accounted for approximately 67%of the total reduction of𝛼α-Fe_(2)O_(3) nanoparticles.The residual reduction of𝛼α-Fe_(2)O_(3) nanoparticles in∆oxpG-omcST strain was likely caused by redox-active substances in cell supernatant.Conversely,the reduction of dissolved Fe(III)was almost unaffected in∆oxpG-omcST strain at the same concentration.However,at high dissolved Fe(III)concentration,the reduction significantly decreased due to the formation of Fe(III)nanoparticles,suggesting that this EET process is specific to Fe(III)nanoparticles.Overall,our study provided a more comprehensive understanding for the EET pathways between G.sulfurreducens PCA and different Fe(III)species,enriching our knowledge on the role of microorganisms in iron biogeochemical cycles and remediation strategies of pollutants.展开更多
Amyotrophic lateral sclerosis(ALS)is a fatal,late-onset neurodegenerative disorder characterized by the progressive degeneration of motor neurons in the motor cortex,brainstem,and spinal cord(Feldman et al.,2022).
A functional interlayer based on two-dimensional(2D)porous modified vermiculite nanosheets(PVS)was obtained by acid-etching vermiculite nanosheets.The as-obtained 2D porous nanosheets exhibited a high specific surface...A functional interlayer based on two-dimensional(2D)porous modified vermiculite nanosheets(PVS)was obtained by acid-etching vermiculite nanosheets.The as-obtained 2D porous nanosheets exhibited a high specific surface area of 427 m^(2)·g^(-1)and rich surface active sites,which help restrain polysulfides(LiPSs)through good physi-cal and chemical adsorption,while simultaneously accelerating the nucleation and dissolution kinetics of Li_(2)S,effec-tively suppressing the shuttle effect.The assembled lithium-sulfur batteries(LSBs)employing the PVS-based inter-layer delivered a high initial discharge capacity of 1386 mAh·g^(-1)at 0.1C(167.5 mAh·g^(-1)),long-term cycling stabil-ity,and good rate property.展开更多
A redox-active monolayer on an optically transparent electrode constitutes a typical platform for spectroelectrochemical sensing.The necessity for its sophistication arises from the availability of multi-dimensional s...A redox-active monolayer on an optically transparent electrode constitutes a typical platform for spectroelectrochemical sensing.The necessity for its sophistication arises from the availability of multi-dimensional sensing signals.Simultaneous monitoring of the redox current and color change synchronized with the oxidation state change significantly enhances sen-sitivity and selectivity.This study aimed to elucidate the modification of an indium tin oxide(ITO)electrode with a viologen monolayer with an ordered orientation.Novel methods were developed to immobilize a viologen molecule bearing a car-boxyl group to form assembled monolayers through a condensation reaction using 1-ethyl-3-(3-dimethylaminopropyl)-car-bodiimide with N-hydroxy-succinimide(EDC/NHS).In the two methods of immobilization,one utilizes a two-step process to firstly form an aromatic siloxane base layer and subsequently attach the viologen derivative through an amide linkage by post-amidation.The other employs a direct ester linkage between the hydroxyl groups of the ITO surface and the car-boxyl group of the viologen derivative.The latter method was also applied to immobilize a ferrocenyl group at a very short distance from the ITO surface.Potential-modulated UV-visible transmission absorption spectral measurement techniques with oblique incidence of plane-polarized light were employed to determine the orientation of the longitudinal axis of the reduced form of the viologen.The frequency dependence data of the potential-modulated transmission absorption signals were utilized to analyze the electron transfer kinetics.The performance of the two viologen-modified electrodes was com-pared to that of an ITO modified by post-amidation to the most commonly used base layer prepared with 3-aminopropyl triethoxysilane.展开更多
Covalent organic frameworks(COFs)are promising materials for mitigating polysulfide shuttling in lithium-sulfur(Li-S)batteries,but enhancing their ability to convert polysulfides across a wide temperature range remain...Covalent organic frameworks(COFs)are promising materials for mitigating polysulfide shuttling in lithium-sulfur(Li-S)batteries,but enhancing their ability to convert polysulfides across a wide temperature range remains a challenge,Herein,we introduce a redox-active COF(RaCOF)that functions as both a physical barrier and a kinetic enhancer to improve the temperature adaptability of Li-S batteries,The RaCOF constructed from redox-active anthraquinone units accelerates polysulfide conversion kinetics through reversible C=O/C-OLi transformations within a voltage range of 1,7 to 2.8 V(vs.Li^(+)/Li),optimizing sulfur redox reactions in ether-based electrolytes.Unlike conventional COFs,RaCOF provides bidentate trapping of polysulfides,increasing binding energy and facilitating more effective polysulfide management.In-situ XRD and ToF-SIMS analyses confirm that RaCOF enhances polysulfide adsorption and promotes the transformation of lithium sulfide(Li_(2)S),leading to better sulfur cathode reutilization.Consequently,RaCOF-modified Li-S batteries demonstrate low self-discharge(4.0%decay over a 7-day rest),excellent wide-temperature performance(stable from-10 to+60℃),and high-rate cycling stability(94%capacity retention over 500 cycles at 5.0 C).This work offers valuable insights for designing COF structures aimed at achieving temperature-adaptive performance in rechargeable batteries.展开更多
The stable operation of supercapacitors at extremely low temperatures is crucial for applications in harsh envi-ronments.Unfortunately,conventional inorganic electrodes suffer from sluggish diffusion kinetics and poor...The stable operation of supercapacitors at extremely low temperatures is crucial for applications in harsh envi-ronments.Unfortunately,conventional inorganic electrodes suffer from sluggish diffusion kinetics and poor cycling stability for proton pseudocapacitors.Here,a redox-active polymer poly(1,5-diaminonaphthalene)is developed and synthesized as an ultrafast,high-mass loading,and durable pseudocapacitive anode.The charge storage of poly(1,5-diaminonaphthalene)depends on the reversible coordination reaction of the C¼N group with Hþ,which enables fast kinetics associated with surface-controlled reactions.The 3D-printed organic electrode delivers a remarkable areal capacitance(8.43 F cm^(-2)at 30.78 mg cm^(-2))and thickness-independent rate per-formance.Furthermore,the 3D-printed proton pseudocapacitor exhibits great low-temperature tolerance and delivers a high energy density of 0.44 mWh cm^(-2)at-60℃,as well as operates well even at-80℃.This work signifies that combining organic material design with 3D hierarchical network electrode construction can provide a promising solution for low-temperature-resistant supercapacitors.展开更多
Lithium-sulfur batteries(LSBs)are considered as the most promising energy storage technologies owing to their large theoretical energy density(2500Wh/kg)and specific capacity(1675 mAh/g).However,the heavy shuttle effe...Lithium-sulfur batteries(LSBs)are considered as the most promising energy storage technologies owing to their large theoretical energy density(2500Wh/kg)and specific capacity(1675 mAh/g).However,the heavy shuttle effect of polysulfides and the growth of lithium dendrites greatly hinder their further development and commercial application.In this paper,cobalt-molybdenum bimetallic carbides heterostructure(Co_(6)Mo_(6)C_(2)@Co@NC)was successfully prepared through chemical etching procedure of ZIF-67 precursor with sodium molybdate and the subsequent high temperature annealing process.The obtained dodecahedral Co_(6)Mo_(6)C_(2)@Co@NC with hollow and porous structure provides large specific surface area and plentiful active sites,which speeds up the chemisorption and catalytic conversion of polysulfides,thus mitigating the shuttle effect of polysulfides and the generation of lithium dendrites.When applied as the LSBs separator modifier layer,the cell with modified separator present excellent rate capability and durable cycling stability.In particular,the cell with Co_(6)Mo_(6)C_(2)@Co@NC/PP separator can maintain the high capacity of 738 mAh/g at the current density of 2 C and the specific capacity of 782.6 mAh/g after 300 cycles at 0.5 C,with the coulombic efficiency(CE)near to 100%.Moreover,the Co_(6)Mo_(6)C_(2)@Co@NC/PP battery exhibits the impressive capacity of 431 mAh/g in high sulfur loading(4.096 mg/cm^(2))at 0.5 C after 200 cycles.This work paves the way for the development of bimetallic carbides heterostructure multifunctional catalysts for durable Li-S battery applications and reveals the synergistic regulation of polysulfides and lithium dendrites through the optimization of the structure and composition.展开更多
Biochar is extensively used as an effective soil amendment for environmental remediation.In addition to its strong contaminant sorption capability, biochar also plays an important role in chemical transformation of co...Biochar is extensively used as an effective soil amendment for environmental remediation.In addition to its strong contaminant sorption capability, biochar also plays an important role in chemical transformation of contaminant due to its inherent redox-active moieties.However, the transformation efficiency of inorganic contaminants is generally very limited when the direct adsorption of contaminants on biochar is inefficient. The present study demonstrates the role of Fe ion as an electron shuttle to enhance Cr(Ⅵ) reduction by biochars. Batch experiments were conducted to examine the effects of Fe(Ⅲ) levels,pyrolysis temperature of biochar, initial solution pH, and biochar dosage on the efficiency of Cr(Ⅵ) removal. Results showed a significant enhancement in Cr(Ⅵ) reduction with an increase in Fe(Ⅲ) concentration and a decrease of initial pH. Biochar produced at higher pyrolysis temperatures(e.g., 700°C) favored Cr(Ⅵ) removal, especially in the presence of Fe(Ⅲ), while a higher biochar dosage proved unfavorable likely due to the agglomeration or precipitation of biochar. Speciation analysis of Fe and Cr elements on the surface of biochar and in the solution further confirmed the role of Fe ion as an electron shuttle between biochar and Cr(Ⅵ). The present findings provide a potential strategy for the advanced treatment of Cr(Ⅵ) at low concentrations as well as an insight into the environmental fate of Cr(Ⅵ) and other micro-pollutants in soil or aqueous compartments containing Fe and natural or engineered carbonaceous materials.展开更多
Lithium-sulfur(Li-S) battery is one of the best candidates for the next-generation energy storage system due to its high theoretical capacity(1675 mA h-1),low cost and environment friendliness.However,lithium(Li) dend...Lithium-sulfur(Li-S) battery is one of the best candidates for the next-generation energy storage system due to its high theoretical capacity(1675 mA h-1),low cost and environment friendliness.However,lithium(Li) dendrites formation and polysulfide shuttle effect are two major challenges that limit the commercialization of Li-S batteries.Here we design a facile bifunctional interlayer of gelatin-based fibers(GFs),aiming to protect the Li anode surface from the dendrites growth and also hinder the polysulfide shuttle effect.We reveal that the 3D structural network of GFs layer with abundant polar sites helps to homogenize Li-ion flux,leading to uniform Li-ion deposition.Meanwhile,the polar moieties also immobilize the lithium polysulfides and protect the Li metal from the side-reaction.As a result,the anodeprotected batteries have shown significantly enhanced performance.A high coulombic efficiency of 96% after 160 cycles has been achieved in the Li-Cu half cells.The Li-Li symmetric cells exhibit a prolonged lifespan for 800 h with voltage hysteresis(10 mV).With the as-prepared GFs layer,the Li-S battery shows approximately 14% higher capacity retention than the pristine battery at 0.5 C after 100 cycles.Our work presents that this gelatin-based bi-functional interlayer provides a viable strategy for the manufacturing of advanced Li-S batteries.展开更多
Developing photosensitizers suitable for the cobalt electrolyte and understanding the structure-property relationship of organic dyes is warranted for the dye-sensitized solar cells （DSSCs）. The DSSCs incorporating ...Developing photosensitizers suitable for the cobalt electrolyte and understanding the structure-property relationship of organic dyes is warranted for the dye-sensitized solar cells （DSSCs）. The DSSCs incorporating tris（1,10-phenanthroline）eobalt（Ⅱ/Ⅲ）-based redox elec- trolyte and four synthesized organic dyes as photosensitizers are described. The photovoltaic performance of these dyes-sensitized solar cells employing the cobalt redox shuttle and the influences of the w-conjugated spacers of organic dyes upon the photovoltage and photocur- rent of mesoscopic titania solar cells are investigated. It is found that organic dyes with thiophene derivates as linkers are suitable for DSSCs employing cobalt electrolytes. DSSCs sensitized with the as-synthesized dyes in combination with the cobalt redox shuttle yield an overall power conversion efficiency of 6.1% under 100 mW/cm2 AM1.5 G illumination.展开更多
Lithium-sulfur battery(LSB) has high energy density but is limited by the polysulfides shuttle and dendrite growth during cycling. Herein, a free-standing cellulose nanofiber(CNF) separator is designed and fabricated ...Lithium-sulfur battery(LSB) has high energy density but is limited by the polysulfides shuttle and dendrite growth during cycling. Herein, a free-standing cellulose nanofiber(CNF) separator is designed and fabricated in isopropanol/water suspension through vacuum filtration progress. CNFs with abundant polar oxygen-containing functional groups can chemically immobilize the polysulfides, and suppress the formation of the dendrites by controlling the surface morphology of the SEI on lithium metal in LSB. The isopropanol content in a suspension can fine-tune the pore structure of the membrane to achieve optimal electrochemical performance. The prepared separator displays integrated advantages of an ultrathin thickness(19 μm), lightweight(0.87 mg cm^(-2)), extremely high porosity(98.05%), and decent electrolyte affinity. As a result, the discharge capacity of the LSB with CNF separator at the first and 100 th cycle is 1.4 and 1.3 times that of PP separator, respectively. Our research provides an environmentalfriendly and facile strategy for the preparation of multifunctional separators for LSBs.展开更多
文摘Herein,3‑aminopropyltriethoxysilane(APTES)was used to modify F‑containing silica slag(SS)by simple grafting and served as a multifunctional barrier layer.The amino group(—NH2)in the amino‑modified SS(NH2‑SS)forms ligand bonds or hydrogen bonds with sulfur ions in lithium polysulfides(LiPSs),thus inhibiting the shuttle effect.Electrochemical analyses demonstrated that lithium‑sulfur(Li‑S)batteries employing the NH2‑SS interlayer exhibited discharge specific capacities of 1048 and 789 mAh·g^(-1) at 0.2C and 2C,respectively,and even at 4C,the initial discharge specific capacity remained at 590 mAh·g^(-1),outperforming the Li‑S battery with unmodified SS as the interlayer.
基金supported by Guangdong Basic and Applied Basic Research Foundation(2025A1515011362)the National Natural Science Foundation of China(52102304,52172238)Open Project of Shaanxi Laboratory of Aerospace Power(2021SXSYS-01-03).
文摘Pb-Sn mixed perovskite solar cells(PSCs)are crucial components for realizing efficient all-perovskite tandem devices.However,their efficiency and stability are severely limited by oxidative degradation(Sn^(4+)formation)and metallic defects(Sn^(0)/Pb^(0)).In addition,the rapid and uncontrolled Sn^(2+)nucleation kinetics result in nonuniform crystallization.Herein,we introduce a natural redox shuttle glutathione(GSH)in Pb-Sn mixed PSCs,achieving regenerable antioxidation and crystallization regulation simultaneously.The reversible redox reactions between GSH and glutathione disulfide(GSSG)enable the self-healing of Sn^(4+)and Sn^(0)/Pb^(0)impurities,creating a regenerable antioxidation protective shell at the perovskite interfaces.Meanwhile,the strong coordination between GSH and perovskite regulates the crystallization process,optimizing the nucleation and crystallization kinetics.Furthermore,the GSH incorporation creates a high-quality charge separation junction at the perovskite/hole transport layer,facilitating carrier separation and extraction.The optimized Pb-Sn PSCs exhibit impressive power conversion efficiencies(PCEs)of up to 23.71%.The champion all-perovskite tandem PSCs with GSH achieve a PCE of 28.49%and retain 90%of the initial PCE after 560 h of continuous illumination.This work establishes a new nature-inspired redox shuttling strategy and elucidates its working mechanism,advancing the development of efficient and stable all-perovskite tandem solar cells.
基金supported by the National Natural Science Foundation of China(52371131)the 10th Youth Talent Lifting Project of the China Association for Science and Technology.
文摘Rechargeable alkali metal-sulfur(M-S)batteries,including Li/Na/K-S chemistries,have the potential to utilize abundant and low-cost sulfur cathodes yet offer high theoretical energy densities.However,their practical electrochemical performance is fundamentally limited by the polysulfide shuttle effect.This challenge is particularly exacerbated in Na-S and K-S systems owing to larger metal-ion radii,weaker solvation energies,slower redox kinetics,and greater electrolyte-electrode incompatibilities compared to Li-S batteries.This review presents a comparative analysis of interface engineering strategies designed to suppress the shuttle effect across these three systems.Following a summary of sulfur cathode properties and reaction mechanisms,we systematically examine the origins of polysulfide shuttling.Our analysis progresses from functional separator design and interlayer enhancements to the implementation of solid-state electrolytes for root-cause inhibition.By evaluating interface engineering research specific to Na-S and K-S batteries,we elucidate both shared principles and unique challenges inherent to alkali M-S systems.Finally,we propose multifaceted solutions to achieve shuttlefree operation and enhance overall battery performance,thereby establishing a foundation for future advancements.
基金the financial support from the Natural Science Foundation of Jiangsu Province(BK20231292)the Jiangsu Agricultural Science and Technology Innovation Fund(CX(24)3091)+6 种基金the Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX25_1429)the National Key R&D Program of China(2024YFE0109200)the Fundamental Research Funds for the Central Universities(No.2024300440)Guangdong Basic and Applied Basic Research Foundation(2025A1515011098)the National Natural Science Foundation of China(12464032)the Natural Science Foundation of Jiangxi Province(20232BAB201032)Ji'an Science and Technology Plan Project(2024H-100301)。
文摘Zn-I_(2) batteries have emerged as promising next-generation energy storage systems owing to their inherent safety,environmental compatibility,rapid reaction kinetics,and small voltage hysteresis.Nevertheless,two critical challenges,i.e.,zinc dendrite growth and polyiodide shuttle effect,severely impede their commercial viability.To conquer these limitations,this study develops a multifunctional separator fabricated from straw-derived carboxylated nanocellulose,with its negative charge density further reinforced by anionic polyacrylamide incorporation.This modification simultaneously improves the separator’s mechanical properties,ionic conductivity,and Zn^(2+)ion transfer number.Remarkably,despite its ultrathin 20μm profile,the engineered separator demonstrates exceptional dendrite suppression and parasitic reaction inhibition,enabling Zn//Zn symmetric cells to achieve impressive cycle life(>1800 h at 2 m A cm^(-2)/2 m Ah cm^(-2))while maintaining robust performance even at ultrahigh areal capacities(25 m Ah cm^(-2)).Additionally,the separator’s anionic characteristic effectively blocks polyiodide migration through electrostatic repulsion,yielding Zn-I_(2) batteries with outstanding rate capability(120.7 m Ah g^(-1)at 5 A g^(-1))and excellent cyclability(94.2%capacity retention after 10,000 cycles).And superior cycling stability can still be achieved under zinc-deficient condition and pouch cell configuration.This work establishes a new paradigm for designing high-performance zinc-based energy storage systems through rational separator engineering.
基金supported by the National Key Research and Development Project(No.2020YFA0907500)the National Natural Science Foundation of China(No.22476206)+1 种基金the supports from the National Young Top-Notch Talents(No.W03070030)Youth Innovation Promotion Association of the Chinese Academy of Sciences(No.Y202011).
文摘Fe reducing bacteria(FRB),through extracellular electron transfer(EET)pathway,can reduce Fe(III)nanoparticles,thereby affecting the migration,transformation,and degradation of pollutants.However,the interaction of Fe(III)nanoparticles with the most commonly identified FRB,Geobacter sulfurreducens PCA,remains poorly understood.Herein,we demonstrated that the synergistic role of outer membrane proteins and periplasmic proteins in the EET process for-Fe_(2)O_(3),Fe3O4,and𝛽α-FeOOH nanoparticles by construction of multiple gene knockout strain.oxpG(involved in the type II secretion system)and omcST(outer membrane c-type cytochrome)medi-ated pathways accounted for approximately 67%of the total reduction of𝛼α-Fe_(2)O_(3) nanoparticles.The residual reduction of𝛼α-Fe_(2)O_(3) nanoparticles in∆oxpG-omcST strain was likely caused by redox-active substances in cell supernatant.Conversely,the reduction of dissolved Fe(III)was almost unaffected in∆oxpG-omcST strain at the same concentration.However,at high dissolved Fe(III)concentration,the reduction significantly decreased due to the formation of Fe(III)nanoparticles,suggesting that this EET process is specific to Fe(III)nanoparticles.Overall,our study provided a more comprehensive understanding for the EET pathways between G.sulfurreducens PCA and different Fe(III)species,enriching our knowledge on the role of microorganisms in iron biogeochemical cycles and remediation strategies of pollutants.
基金supported by the Else Kröner-Fresenius-Stiftung(2021-EKSE.95)the Deutsche Forschungsgemeinschaft(CRC1678 and Germany’s Excellence Strategy-CECAD,EXC 2030-390661388)(to DV).
文摘Amyotrophic lateral sclerosis(ALS)is a fatal,late-onset neurodegenerative disorder characterized by the progressive degeneration of motor neurons in the motor cortex,brainstem,and spinal cord(Feldman et al.,2022).
文摘A functional interlayer based on two-dimensional(2D)porous modified vermiculite nanosheets(PVS)was obtained by acid-etching vermiculite nanosheets.The as-obtained 2D porous nanosheets exhibited a high specific surface area of 427 m^(2)·g^(-1)and rich surface active sites,which help restrain polysulfides(LiPSs)through good physi-cal and chemical adsorption,while simultaneously accelerating the nucleation and dissolution kinetics of Li_(2)S,effec-tively suppressing the shuttle effect.The assembled lithium-sulfur batteries(LSBs)employing the PVS-based inter-layer delivered a high initial discharge capacity of 1386 mAh·g^(-1)at 0.1C(167.5 mAh·g^(-1)),long-term cycling stabil-ity,and good rate property.
基金supports by the Grant-in-Aid of Scientific Research of Challenging Research(Exploratory)(JP23K17738)to TS from MEXT of Japanthe 41st grant of research from Nippon Sheet Glass Foundation for Materials Science and Engineering to TS.
文摘A redox-active monolayer on an optically transparent electrode constitutes a typical platform for spectroelectrochemical sensing.The necessity for its sophistication arises from the availability of multi-dimensional sensing signals.Simultaneous monitoring of the redox current and color change synchronized with the oxidation state change significantly enhances sen-sitivity and selectivity.This study aimed to elucidate the modification of an indium tin oxide(ITO)electrode with a viologen monolayer with an ordered orientation.Novel methods were developed to immobilize a viologen molecule bearing a car-boxyl group to form assembled monolayers through a condensation reaction using 1-ethyl-3-(3-dimethylaminopropyl)-car-bodiimide with N-hydroxy-succinimide(EDC/NHS).In the two methods of immobilization,one utilizes a two-step process to firstly form an aromatic siloxane base layer and subsequently attach the viologen derivative through an amide linkage by post-amidation.The other employs a direct ester linkage between the hydroxyl groups of the ITO surface and the car-boxyl group of the viologen derivative.The latter method was also applied to immobilize a ferrocenyl group at a very short distance from the ITO surface.Potential-modulated UV-visible transmission absorption spectral measurement techniques with oblique incidence of plane-polarized light were employed to determine the orientation of the longitudinal axis of the reduced form of the viologen.The frequency dependence data of the potential-modulated transmission absorption signals were utilized to analyze the electron transfer kinetics.The performance of the two viologen-modified electrodes was com-pared to that of an ITO modified by post-amidation to the most commonly used base layer prepared with 3-aminopropyl triethoxysilane.
基金funding supporting from the National Natural Science Foundation of China(22309003,22379001)the Natural Science Research Project of Anhui Province Education Department(2023AH051119)+3 种基金the open project funding from Shanghai Key Laboratory of Multi phase Materials Chemical Engineering(MMCE2024001)the National Key Research and Development Program of China(2022YFB2402201)the Shanghai Pilot Program for Basic Research-Fudan University 21TQ1400100(21TQ009)the Fundamental Research Funds for the Central Universities(20720220010).
文摘Covalent organic frameworks(COFs)are promising materials for mitigating polysulfide shuttling in lithium-sulfur(Li-S)batteries,but enhancing their ability to convert polysulfides across a wide temperature range remains a challenge,Herein,we introduce a redox-active COF(RaCOF)that functions as both a physical barrier and a kinetic enhancer to improve the temperature adaptability of Li-S batteries,The RaCOF constructed from redox-active anthraquinone units accelerates polysulfide conversion kinetics through reversible C=O/C-OLi transformations within a voltage range of 1,7 to 2.8 V(vs.Li^(+)/Li),optimizing sulfur redox reactions in ether-based electrolytes.Unlike conventional COFs,RaCOF provides bidentate trapping of polysulfides,increasing binding energy and facilitating more effective polysulfide management.In-situ XRD and ToF-SIMS analyses confirm that RaCOF enhances polysulfide adsorption and promotes the transformation of lithium sulfide(Li_(2)S),leading to better sulfur cathode reutilization.Consequently,RaCOF-modified Li-S batteries demonstrate low self-discharge(4.0%decay over a 7-day rest),excellent wide-temperature performance(stable from-10 to+60℃),and high-rate cycling stability(94%capacity retention over 500 cycles at 5.0 C).This work offers valuable insights for designing COF structures aimed at achieving temperature-adaptive performance in rechargeable batteries.
基金supported by National Natural Science Foundation of China(52072173)International Science and Technology cooperation program of Jiangsu Province(SBZ2022000084)Funding for Outstanding Doctoral Dissertation in NUAA(BCXJ23-10).
文摘The stable operation of supercapacitors at extremely low temperatures is crucial for applications in harsh envi-ronments.Unfortunately,conventional inorganic electrodes suffer from sluggish diffusion kinetics and poor cycling stability for proton pseudocapacitors.Here,a redox-active polymer poly(1,5-diaminonaphthalene)is developed and synthesized as an ultrafast,high-mass loading,and durable pseudocapacitive anode.The charge storage of poly(1,5-diaminonaphthalene)depends on the reversible coordination reaction of the C¼N group with Hþ,which enables fast kinetics associated with surface-controlled reactions.The 3D-printed organic electrode delivers a remarkable areal capacitance(8.43 F cm^(-2)at 30.78 mg cm^(-2))and thickness-independent rate per-formance.Furthermore,the 3D-printed proton pseudocapacitor exhibits great low-temperature tolerance and delivers a high energy density of 0.44 mWh cm^(-2)at-60℃,as well as operates well even at-80℃.This work signifies that combining organic material design with 3D hierarchical network electrode construction can provide a promising solution for low-temperature-resistant supercapacitors.
基金supported by National Natural Science Foundation of China(Nos.52472194,52101243)Natural Science Foundation of Guangdong Province,China(No.2023A1515012619)the Science and Technology Planning Project of Guangzhou(No.202201010565).
文摘Lithium-sulfur batteries(LSBs)are considered as the most promising energy storage technologies owing to their large theoretical energy density(2500Wh/kg)and specific capacity(1675 mAh/g).However,the heavy shuttle effect of polysulfides and the growth of lithium dendrites greatly hinder their further development and commercial application.In this paper,cobalt-molybdenum bimetallic carbides heterostructure(Co_(6)Mo_(6)C_(2)@Co@NC)was successfully prepared through chemical etching procedure of ZIF-67 precursor with sodium molybdate and the subsequent high temperature annealing process.The obtained dodecahedral Co_(6)Mo_(6)C_(2)@Co@NC with hollow and porous structure provides large specific surface area and plentiful active sites,which speeds up the chemisorption and catalytic conversion of polysulfides,thus mitigating the shuttle effect of polysulfides and the generation of lithium dendrites.When applied as the LSBs separator modifier layer,the cell with modified separator present excellent rate capability and durable cycling stability.In particular,the cell with Co_(6)Mo_(6)C_(2)@Co@NC/PP separator can maintain the high capacity of 738 mAh/g at the current density of 2 C and the specific capacity of 782.6 mAh/g after 300 cycles at 0.5 C,with the coulombic efficiency(CE)near to 100%.Moreover,the Co_(6)Mo_(6)C_(2)@Co@NC/PP battery exhibits the impressive capacity of 431 mAh/g in high sulfur loading(4.096 mg/cm^(2))at 0.5 C after 200 cycles.This work paves the way for the development of bimetallic carbides heterostructure multifunctional catalysts for durable Li-S battery applications and reveals the synergistic regulation of polysulfides and lithium dendrites through the optimization of the structure and composition.
基金supported by the National Key Research and Development Program of China (No. 2016YFA0203102)the National Basic Research Program of China (No. 2015CB932003)+1 种基金the National Natural Science Foundation of China (Nos. 21777173, 21522705)the support from the Youth Innovation Promotion Association CAS
文摘Biochar is extensively used as an effective soil amendment for environmental remediation.In addition to its strong contaminant sorption capability, biochar also plays an important role in chemical transformation of contaminant due to its inherent redox-active moieties.However, the transformation efficiency of inorganic contaminants is generally very limited when the direct adsorption of contaminants on biochar is inefficient. The present study demonstrates the role of Fe ion as an electron shuttle to enhance Cr(Ⅵ) reduction by biochars. Batch experiments were conducted to examine the effects of Fe(Ⅲ) levels,pyrolysis temperature of biochar, initial solution pH, and biochar dosage on the efficiency of Cr(Ⅵ) removal. Results showed a significant enhancement in Cr(Ⅵ) reduction with an increase in Fe(Ⅲ) concentration and a decrease of initial pH. Biochar produced at higher pyrolysis temperatures(e.g., 700°C) favored Cr(Ⅵ) removal, especially in the presence of Fe(Ⅲ), while a higher biochar dosage proved unfavorable likely due to the agglomeration or precipitation of biochar. Speciation analysis of Fe and Cr elements on the surface of biochar and in the solution further confirmed the role of Fe ion as an electron shuttle between biochar and Cr(Ⅵ). The present findings provide a potential strategy for the advanced treatment of Cr(Ⅵ) at low concentrations as well as an insight into the environmental fate of Cr(Ⅵ) and other micro-pollutants in soil or aqueous compartments containing Fe and natural or engineered carbonaceous materials.
基金supported by the National Natural Science Foundation of China (No. 51861165101)。
文摘Lithium-sulfur(Li-S) battery is one of the best candidates for the next-generation energy storage system due to its high theoretical capacity(1675 mA h-1),low cost and environment friendliness.However,lithium(Li) dendrites formation and polysulfide shuttle effect are two major challenges that limit the commercialization of Li-S batteries.Here we design a facile bifunctional interlayer of gelatin-based fibers(GFs),aiming to protect the Li anode surface from the dendrites growth and also hinder the polysulfide shuttle effect.We reveal that the 3D structural network of GFs layer with abundant polar sites helps to homogenize Li-ion flux,leading to uniform Li-ion deposition.Meanwhile,the polar moieties also immobilize the lithium polysulfides and protect the Li metal from the side-reaction.As a result,the anodeprotected batteries have shown significantly enhanced performance.A high coulombic efficiency of 96% after 160 cycles has been achieved in the Li-Cu half cells.The Li-Li symmetric cells exhibit a prolonged lifespan for 800 h with voltage hysteresis(10 mV).With the as-prepared GFs layer,the Li-S battery shows approximately 14% higher capacity retention than the pristine battery at 0.5 C after 100 cycles.Our work presents that this gelatin-based bi-functional interlayer provides a viable strategy for the manufacturing of advanced Li-S batteries.
基金This work was supported by the National Natu- ral Science Foundation of China （No.21072152 and No.21101115）.
文摘Developing photosensitizers suitable for the cobalt electrolyte and understanding the structure-property relationship of organic dyes is warranted for the dye-sensitized solar cells （DSSCs）. The DSSCs incorporating tris（1,10-phenanthroline）eobalt（Ⅱ/Ⅲ）-based redox elec- trolyte and four synthesized organic dyes as photosensitizers are described. The photovoltaic performance of these dyes-sensitized solar cells employing the cobalt redox shuttle and the influences of the w-conjugated spacers of organic dyes upon the photovoltage and photocur- rent of mesoscopic titania solar cells are investigated. It is found that organic dyes with thiophene derivates as linkers are suitable for DSSCs employing cobalt electrolytes. DSSCs sensitized with the as-synthesized dyes in combination with the cobalt redox shuttle yield an overall power conversion efficiency of 6.1% under 100 mW/cm2 AM1.5 G illumination.
基金supported by the National Key Research and Development Program(2018YFB1501500)the National Science Foundation for Excellent Young Scholars of China(21922815)+2 种基金the National Key Research and Development(R&D)Program of China(2020YFB1505800)the Research and Development Project of Key Core and Common Technology of Shanxi Province(2020XXX014)the Fundamental Research Program of Shanxi Province(20210302123008,20210302124101)。
文摘Lithium-sulfur battery(LSB) has high energy density but is limited by the polysulfides shuttle and dendrite growth during cycling. Herein, a free-standing cellulose nanofiber(CNF) separator is designed and fabricated in isopropanol/water suspension through vacuum filtration progress. CNFs with abundant polar oxygen-containing functional groups can chemically immobilize the polysulfides, and suppress the formation of the dendrites by controlling the surface morphology of the SEI on lithium metal in LSB. The isopropanol content in a suspension can fine-tune the pore structure of the membrane to achieve optimal electrochemical performance. The prepared separator displays integrated advantages of an ultrathin thickness(19 μm), lightweight(0.87 mg cm^(-2)), extremely high porosity(98.05%), and decent electrolyte affinity. As a result, the discharge capacity of the LSB with CNF separator at the first and 100 th cycle is 1.4 and 1.3 times that of PP separator, respectively. Our research provides an environmentalfriendly and facile strategy for the preparation of multifunctional separators for LSBs.
