Anion-exchange membrane water electrolysers(AEMWEs)and fuel cells(AEMFCs)are critical technologies for converting renewable resources into green hydrogen(H_(2)),where anion-exchange membranes(AEMs)play a vital role in...Anion-exchange membrane water electrolysers(AEMWEs)and fuel cells(AEMFCs)are critical technologies for converting renewable resources into green hydrogen(H_(2)),where anion-exchange membranes(AEMs)play a vital role in efficiently transporting hydroxide ions(OH^(-))and minimizing fuel crossover,thus enhancing overall efficiency.While conventional AEMs with linear,side-chain,and block polymer architectures show promise through functionalization,their long-term performance remains a concern.To address this,hyperbranched polymers offer a promising alternative due to their three-dimensional structure,higher terminal functionality,and ease of functionalization.This unique architecture provides interconnected ion transport pathways,fractional free volume,and enhanced long-term stability in alkaline environments.Recent studies have achieved conductivities as high as 304.5 mS cm^(-1),attributed to their improved fractional free volume and microphase separation in hyperbranched AEMs.This review explores the chemical,mechanical,and ionic properties of hyperbranched AEMs in AEMFCs and assesses their potential for application in AEMWEs.Strategies such as blending and structural functionalisation have significantly improved the properties by promoting microphase separation and increasing the density of cationic groups on the polymer surface.The review provides essential insights for future research,highlighting the challenges and opportunities in developing high-performance hyperbranched AEMs to advance hydrogen energy infrastructure.展开更多
Transition metal-based compounds can serve as pre-catalysts to obtain genuine oxygen evolution reaction(OER)electrocatalysts in the form of oxyhydroxides through electrochemical activation.However,the role and existen...Transition metal-based compounds can serve as pre-catalysts to obtain genuine oxygen evolution reaction(OER)electrocatalysts in the form of oxyhydroxides through electrochemical activation.However,the role and existence form of leached oxygen anions are still controversial.Herein,we selected iron selenite-wrapped hydrated nickel molybdate(denoted as NiMoO/FeSeO)as a pre-catalyst to study the oxyanion effect.It is surprising to find that SeO_(2)-exists in the catalyst in the form of intercalation,which is different from previous studies that suggest that anions are doped with residual elements after electrochemical activation,or adsorbed on the catalyst surface.The experiment and theoretical calculations show that the existence of SeO_(4)^(2-)intercalation effectively adjusts the electronic structure of NiFeOOH,promotes intramolecular electron transfer and O-O release,and thus lowers the reaction energy barrier.As expected,the synthesized NiFeOOH-SeO only needs 202 and 285 mV to attain 100 and 1000 mA cm^(-2)in 1 M KOH.Further,the anion exchange membrane water electrolyzer(AEMWE)consisting of NiFeOOHSeO anode and Pt/C cathode can reach 1 A cm^(-2)at 1.70 V and no significant attenuation within 300 h.Our findings provide insights into the mechanism,by which the intercalated oxyanions enhance the OER performance of NiFeOOH,thereby facilitating large-scale hydrogen production through AEMWE.展开更多
Oxygen evolution reaction(OER)is often regarded as a crucial bottleneck in the field of renewable energy storage and conversion.To further accelerate the sluggish kinetics of OER,a cation and anion modulation strategy...Oxygen evolution reaction(OER)is often regarded as a crucial bottleneck in the field of renewable energy storage and conversion.To further accelerate the sluggish kinetics of OER,a cation and anion modulation strategy is reported here,which has been proven to be effective in preparing highly active electrocatalyst.For example,the cobalt,sulfur,and phosphorus modulated nickel hydroxide(denoted as NiCoPSOH)only needs an overpotential of 232 mV to reach a current density of 20 mA cm^(–2),demonstrating excellent OER performances.The cation and anion modulation facilitates the generation of high-valent Ni species,which would activate the lattice oxygen and switch the OER reaction pathway from conventional adsorbate evolution mechanism to lattice oxygen mechanism(LOM),as evidenced by the results of electrochemical measurements,Raman spectroscopy and differential electrochemical mass spectrometry.The LOM pathway of NiCoPSOH is further verified by the theoretical calculations,including the upshift of O 2p band center,the weakened Ni–O bond and the lowest energy barrier of rate-limiting step.Thus,the anion and cation modulated catalyst NiCoPSOH could effectively accelerate the sluggish OER kinetics.Our work provides a new insight into the cation and anion modulation,and broadens the possibility for the rational design of highly active electrocatalysts.展开更多
Ischemia–reperfusion injury is a common pathophysiological mechanism in retinal degeneration.PANoptosis is a newly defined integral form of regulated cell death that combines the key features of pyroptosis,apoptosis,...Ischemia–reperfusion injury is a common pathophysiological mechanism in retinal degeneration.PANoptosis is a newly defined integral form of regulated cell death that combines the key features of pyroptosis,apoptosis,and necroptosis.Oligomerization of mitochondrial voltage-dependent anion channel 1 is an important pathological event in regulating cell death in retinal ischemia–reperfusion injury.However,its role in PANoptosis remains largely unknown.In this study,we demonstrated that voltage-dependent anion channel 1 oligomerization-mediated mitochondrial dysfunction was associated with PANoptosis in retinal ischemia–reperfusion injury.Inhibition of voltage-dependent anion channel 1 oligomerization suppressed mitochondrial dysfunction and PANoptosis in retinal cells subjected to ischemia–reperfusion injury.Mechanistically,mitochondria-derived reactive oxygen species played a central role in the voltagedependent anion channel 1-mediated regulation of PANoptosis by promoting PANoptosome assembly.Moreover,inhibiting voltage-dependent anion channel 1 oligomerization protected against PANoptosis in the retinas of rats subjected to ischemia–reperfusion injury.Overall,our findings reveal the critical role of voltage-dependent anion channel 1 oligomerization in regulating PANoptosis in retinal ischemia–reperfusion injury,highlighting voltage-dependent anion channel 1 as a promising therapeutic target.展开更多
Designing transition metal nickel-cobalt-based battery-type electrode materials driven by anions is crucial for achieving rapid OH-ion transport under electrochemical activation conditions,thereby improving capacitanc...Designing transition metal nickel-cobalt-based battery-type electrode materials driven by anions is crucial for achieving rapid OH-ion transport under electrochemical activation conditions,thereby improving capacitance performance.Herein,borate anions are selected through theoretical calculations,and twodimensional(2D)defect-rich amorphous nickel-cobalt-based borate is synthesized via a facile chemical reduction method.Under potentiostatic modification,activated products(NCB-G-E)are obtained.In situ Raman spectra reveal that electron-deficient borate extracts electrons from metal centers,facilitating the oxidation state transition of Ni and Co.Theoretical calculations show that in situ adsorbed borate regulates the d-band centers of metal sites,enhancing OH^(-)intermediate adsorption.Meanwhile,borate anion adsorption accelerates the deprotonation and activation processes.Electrochemical tests demonstrate that NCB-G-E displays superior capacitance performance,with a high quality specific capacity of383.3 mA h g^(-1)and 65% retention rate at 30 A g^(-1),surpassing most nickel-cobalt-based electrodes.The assembled asymmetric supercapacitor presents an impressive energy density of 68.2 Wh kg^(-1)and good cycling stability.This work highlights the role of electron-deficient borate in tuning metal band structure and promoting oxidation state transition through synergistic defect advantages,offering new prospects for advanced battery-type energy storage materials.展开更多
Electrides,characterized by spatially confined anionic electrons,have emerged as a promising class of materials for catalysis,magnetism,and superconductivity.However,transition-metal-based electrides with diverse elec...Electrides,characterized by spatially confined anionic electrons,have emerged as a promising class of materials for catalysis,magnetism,and superconductivity.However,transition-metal-based electrides with diverse electron dimensionalities remain largely unexplored.Here,we perform a comprehensive first-principles investigation of Y-Co electrides,focusing on Y_(3)Co,Y_(3)Co_(2),and YCo.Our calculations reveal a striking dimensional evolution of anionic electrons:from two-dimensional(2D)confinement in YCo to one-dimensional(1D)in Y_(3)Co_(2)and zero-dimensional(0D)in Y_(3)Co.Remarkably,the YCo monolayer exhibits intrinsic ferromagnetism,with a magnetic moment of 0.65μB per formula unit arising from spin-polarized anionic electrons mediating long-range coupling between Y and Co ions.The monolayer also shows a low exfoliation energy(1.66 J/m^(2)),indicating experimental feasibility.All three electrides exhibit low work functions(2.76 eV-3.11 eV)along with Co-centered anionic states.This work expands the family of transition-metal-based electrides and highlights dimensionality engineering as a powerful strategy for tuning electronic and magnetic properties.展开更多
Electrolytes are crucial components in electrochemical energy storage devices,sparking considerable research interest.However,the significance of anions in the electrolytes is often underestimated.In fact,the anions h...Electrolytes are crucial components in electrochemical energy storage devices,sparking considerable research interest.However,the significance of anions in the electrolytes is often underestimated.In fact,the anions have significant impacts on the performance and stability of lithium batteries.Therefore,comprehensively understanding anion chemistry in electrolytes is of crucial importance.Herein,indepth comprehension of anion chemistry and its positive effects on the interface,solvation structure of Li-ions,as well as the electrochemical performance of the batteries have been emphasized and summarized.This review aims to present a full scope of anion chemistry and furnish systematic cognition for the rational design of advanced electrolytes for better lithium batteries with high energy density,lifespan,and safety.Furthermore,insightful analysis and perspectives based on the current research are proposed.We hope that this review sheds light on new perspectives on understanding anion chemistry in electrolytes.展开更多
Anion modification has been considered as a strategy to improve water splitting efficiency upon oxygen evolution reaction(OER).However,constructing a novel catalysis system with high catalytic activity and precise str...Anion modification has been considered as a strategy to improve water splitting efficiency upon oxygen evolution reaction(OER).However,constructing a novel catalysis system with high catalytic activity and precise structures is still a huge challenge due to the tedious procedure of precursor synthesis and anion selection.Here,a bimetallic(FeNi)nanowire self-assembled superstructure was synthesized using the Hoffmann rearrangement method,and then functionalized with four anions(P,Se,S,and O).Notably,the Fe_(3)Se_(4)/Ni_(3)Se_(4) catalyst shows a high conductivity,enhances the adsorption of intermediate products,accelerates the rate-determining step,and consequently results to improved electrocatalytic performance.Using the Fe_(3)Se_(4)/Ni_(3)Se_(4) catalyst exhibits enhanced performance with overpotential of 316mV at 10 mA/cm^(2),in stark contrast to Fe_(2) P/Ni_(2)P(357mV),Fe_(7)S_(8)/NiS(379 mV),and Fe_(3)O_(4)/NiO(464 mV).Moreover,the formation mechanism of superstructure and the relationship between electronegativities and electrocatalytic properties,are elucidated.Accordingly,this work provides an efficient approach to Hoffmann-type coordination polymer catalyst for oxygen evolution towards a near future.展开更多
Na_(3)V_(2)(PO_(4))_(2)O_(2)F (VP) is recognized as a promising cathode material for sodium-ion batteries due to its stable structural framework and high specific capacity.Density functional theory (DFT) and finite el...Na_(3)V_(2)(PO_(4))_(2)O_(2)F (VP) is recognized as a promising cathode material for sodium-ion batteries due to its stable structural framework and high specific capacity.Density functional theory (DFT) and finite element simulations show that incorporating SO_(4)^(2-)into VP decreases its band gap,lowers the migration energy barrier,and ensures a uniform Na+concentration gradient and stress distribution during charge and discharge cycles.Consequently,the average Na+diffusion coefficient of Na_(3)V_(2)(PO_(4))_(1.95)(SO_(4))_(0.05)O_(2)F(VPS-1) is roughly double that of VP,leading to enhanced rate capability (80 C,75.5 mAh g^(-1)) and cycling stability (111.0 mAh g^(-1)capacity after 1000 cycles at 10 C current density) for VPS-1.VPS-1 exhibits outstanding fast-charging capabilities,achieving an 80%state of charge in just 8.1 min.The assembled VPS-1//SbSn/NPC full cell demonstrated stable cycling over 200 cycles at a high 5 C current,maintaining an average coulombic efficiency of 95.35%.展开更多
Lithium (Li) metal batteries (LMBs) featuring ultrahigh energy densities are expected as ones of the mostprominent devices for future energy storage applications. Nevertheless, the practical application of LMBs is sti...Lithium (Li) metal batteries (LMBs) featuring ultrahigh energy densities are expected as ones of the mostprominent devices for future energy storage applications. Nevertheless, the practical application of LMBs is stillplagued by the poor interfacial stability of Li metal anode. Inorganic-rich interlayer derived from anion decom-positionin advanced liquid electrolytes is demonstrated as an efficient approach to stabilize the Li metal anode,however, is electrolyte-dependent with limited application conditions due to inappropriate electrolyte properties.Herein, an efficient structuration strategy is proposed to fabricate an electrolyte-independent and sustainedinorganic-rich layer, by embedding a type of functional anion aggregates consisting of selected anions ionicallybonded to polymerized cation clusters. The anion aggregates can progressively release anions to react with Liþand form key components boosting the structural stability and Liþ transfer ability of the artificial layer uponcycling. This self-reinforcing working mechanism endows the artificial layer with a sustained inorganic-richnature and promising Li protective ability during long-term cycling, while the electrolyte-independent propertyenables its applications in LMBs using conventional low concentration electrolytes and all-solid-state LMBs withsignificantly enhanced performances. This strategy establishes an alternative designing route of Li protectivelayers for reliable LMBs.展开更多
The poor electrode/electrolyte interface compatibility and inferior electrolyte oxidative tolerance in commercial ethylene carbonate(EC)-based electrolytes have hindered the development of high-voltage sodium-ion batt...The poor electrode/electrolyte interface compatibility and inferior electrolyte oxidative tolerance in commercial ethylene carbonate(EC)-based electrolytes have hindered the development of high-voltage sodium-ion batteries(SIBs).In this study,an anionic chemistry strategy is proposed to strengthen Na^(+)-anion coordination in the solvation sheath,and subsequently reduce the coordination numbers of EC solvents with the addition of NaClO_(4)into NaPF_(6)/EC/DEC electrolytes.Theoretical and experimental results confirm that the competitive coordination capabilities of Na^(+)-ClO_(4)^(-),with high binding energy,induce a wide electrochemical window up to 4.8 V,highly reversible Na^(+)plating/stripping,and fast desolvation kinetics at the electrode/electrolyte interface,thereby hindering the continuous electrolyte decomposition.The optimized electrolyte PEDCF-0.20 demonstrates weakened Na^(+)-EC coordination,increased interaction of Na^(+)-anion in solvation,facilitating the formation of an inorganic-rich interface layer.Consequently,a 2.1 A h cylindrical full cell of hard carbon//NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)delivers an impressive capacity retention of 93.7% after 300 cycles at an extended charging cutoff voltage of 4.1 V.This work provides a new insight into regulating the competitive coordination of anions to guarantee the remarkable cycling stability of high-voltage SIBs.展开更多
The prediction of new fluorooxoborates as ultraviolet(UV)/deep ultraviolet(DUV)opto-electronic functional materials from a largely unexplored chemical space is a challenging task.It has been suggested that the anionic...The prediction of new fluorooxoborates as ultraviolet(UV)/deep ultraviolet(DUV)opto-electronic functional materials from a largely unexplored chemical space is a challenging task.It has been suggested that the anionic frameworks formed by B–O and B–O–F units significantly determine the physical properties of fluorooxoborates.Therefore,the rational design of anionic frameworks could facilitate the materials discovery process.Herein,we propose that a candidate anionic framework can be efficiently derived from an existing one by slightly altering its oxygen content.Following this idea,we hypothesized the existence of a 1D[B_(3)O_(5)F]_(∞)chain from the wellknown 2D[B_(6)O_(9)F_(2_)]_(∞)layer.Accordingly,seven CaB_(3)O_(5)F structures with the expected anionic framework were successfully predicted.First-principles calculations show that all these structures have potential in the UV/DUV birefringent or nonlinear optical(NLO)material field,indicating that the 1D[B_(3)O_(5)F]_(∞)chain is indeed a promising anionic framework for achieving UV/DUV birefringent and NLO performance.展开更多
In the realm of sodium-ion batteries(SIBs),Mn-based layered oxide cathodes have garnered considerable attention owing to their anionic redox reactions(ARRs).Compared to other types of popular sodium-ion cathodes,Mn-ba...In the realm of sodium-ion batteries(SIBs),Mn-based layered oxide cathodes have garnered considerable attention owing to their anionic redox reactions(ARRs).Compared to other types of popular sodium-ion cathodes,Mn-based layered oxide cathodes with ARRs exhibit outstanding specific capacity and energy density,making them promising for SIB applications.However,these cathodes still face some scientific challenges that need to be addressed.This review systematically summarizes the composition,structure,oxygen-redox mechanism,and performance of various types of Mn-based cathodes with ARRs,as well as the main scientific challenges they face,including sluggish ion diffusion,cationic migration,O_(2) release,and element dissolution.Currently,to resolve these challenges,efforts mainly focus on six aspects:synthesis methods,structural design,doped modification,electrolyte design,and surface engineering.Finally,this review provides new insights for future direction,encompassing both fundamental research,such as novel cathode types,interface optimization,and interdisciplinary research,and considerations from an industrialization perspective,including scalability,stability,and safety.展开更多
The two-dimensional MoSe_(2)possesses a large interlayer spacing(0.65 nm)and a narrow bandgap(1.1 eV),showing potential in sodium-ion storage.However,it faces slow kinetics and volume stress during Na^(+)(de)intercala...The two-dimensional MoSe_(2)possesses a large interlayer spacing(0.65 nm)and a narrow bandgap(1.1 eV),showing potential in sodium-ion storage.However,it faces slow kinetics and volume stress during Na^(+)(de)intercalation process,thereby affecting the cycling stability and lifespan of sodium-ion batteries(SIBs).In this work,a novel approach involving anionic doping and structural design has been proposed,wherein a two-step in-situ selenization and surface thermal annealing doping process is applied to fabricate a novel configuration material of fluorine-doped MoSe_(2)@nitrogen-doped carbon nanosheets(F-MoSe_(2)@FNC).The obtained F-MoSe_(2)@FNC,benefiting from the dual advantages of structure and F-doping,synergistically promotes and accelerates the stable(de)intercalation of Na^(+).Henceforth,F-MoSe_(2)@FNC demonstrates notable characteristics in terms of reversible specific capacity,boasting a high initial coulombic efficiency of 76.97%,alongside remarkable rate capabilities and cyclic stability.The constructed F-MoSe_(2)@FNC anode-based half cell manifests exceptional longevity,enduring up to 2550 cycles at 10 A·g^(-1)with a specific capacity of 322.04 mAh·g^(-1).Its electrochemical performance surpasses that of MoSe_(2)@NC and Pure MoSe_(2),underscoring the significance of the proposed synergistic modulation.Through comprehensive kinetic analyses,encompassing in-situ electrochemical impedance spectroscopy(EIS),it is elucidated that the F-MoSe_(2)@FNC electrode showcases elevated pseudo-capacitance and rapid diffusion attributes during charge and discharge processes.Furthermore,the assembled full-cell(F-MoSe_(2)@FNC//Na_(3)V_(2)(PO_(4))_(3))attains a notable energy density of 166.94 Wh·kg^(-1).This design provides insights for the optimization of MoSe_(2)electrodes and their applications in SIBs.展开更多
The photocatalytic reduction of CO_(2)is a crucial area of research aimed at addressing the dual challenges of mitigating rising CO_(2)emissions and producing sustainable chemical feedstocks.While multielectron reduct...The photocatalytic reduction of CO_(2)is a crucial area of research aimed at addressing the dual challenges of mitigating rising CO_(2)emissions and producing sustainable chemical feedstocks.While multielectron reduction pathways for CO_(2)are well explored,the single electron reduction to produce the highly reactive carbon dioxide radical anion(CO_(2)^(·-))remains challenging yet promising for green organic transformations.This review contributes to the field by providing a comprehensive analysis of the mechanisms,materials,and reaction pathways involved in CO_(2)^(·-)generation,focusing on the use of visible-lightdriven photocatalytic materials to circumvent the need for high-energy ultraviolet irradiation.Through a systematic examination of CO_(2)^(·-)production,detection methods,and chemical utilization in photocatalytic carboxylation reactions,this review advances understanding of the chemistry of CO_(2)^(·-)and its applications in sustainable chemical synthesis.In addition,it highlights existing key challenges,such as redox potential limitations,and proposes strategies for scaling up photocatalytic systems to enable practical application.By illuminating the pathway to effectively photocatalyze CO_(2)^(·-)generation and its transformative potential in sustainable chemical synthesis,this review equips scientists with critical insights and strategic approaches for overcoming current limitations,driving innovation in photocatalytic materials for solar-to-chemical energy conversion.展开更多
Anionic redox reaction(ARR)can provide extra capacity beyond transition metal(TM)redox in lithium-rich TM oxide cathodes.Practical ARR application is much hindered by the structure instability,particularly at the surf...Anionic redox reaction(ARR)can provide extra capacity beyond transition metal(TM)redox in lithium-rich TM oxide cathodes.Practical ARR application is much hindered by the structure instability,particularly at the surface.Oxygen release has been widely accepted as the ringleader of surficial structure instability.However,the role of TM in surface stability has been much overlooked,not to mention its interplay with oxygen release.Herein,TM dissolution and oxygen release are comparatively investigated in Li_(1.2)Ni_(0.2)Mn_(0.6)O_(2).Ni is verified to detach from the lattice counter-intuitively despite the overwhelming stoichiometry of Mn,facilitating subsequent oxygen release of the ARR process.Intriguingly,surface reorganization occurs following regulated Ni dissolution,enabling the stabilization of the surface and elimination of oxygen release in turn.Accordingly,a novel optimization strategy is proposed by adding a relaxation step at 4.50 V within the first cycle procedure.Battery performance can be effectively improved,with voltage decay suppressed from 3.44 mV/cycle to 1.60 mV/cycle,and cycle stability improved from 66.77%to 90.01%after 100 cycles.This work provides new perspectives for clarifying ARR surface instability and guidance for optimizing ARR performance.展开更多
P3-type manganese-iron-based cathodes with high specific capacity and abundant resource have attracted considerable attention for sodium-ion batteries.However,the long-term cycle stability of P3-type cathodes is still...P3-type manganese-iron-based cathodes with high specific capacity and abundant resource have attracted considerable attention for sodium-ion batteries.However,the long-term cycle stability of P3-type cathodes is still not satisfactory.In this work,we design a new quaternary manganese-iron-based cathode material(P3-Na_(0.54)Mn_(0.64)Fe_(_(0.1)6)Mg_(0.1)Cu_(0.1)O_(2))by Cu substitution.The strong covalent Cu-O bonds improve the structural stability and the reversibility of O redox during charge and discharge processes.Cu substitution also mitigates the structure change with less unit cell volume variation,and improves the Na-ion transport kinetics effectively.As a result,NMFMC delivers much improved cycling stability and rate capability compared with NMFM.It reveals that the charge compensation of NMFMC is mainly contributed by Mn^(3+/4+),Fe^(3+/3.5+)and O_(2-/-)during the charge and discharge processes,and Cu substitution can also enhance the activity and reversibility of Fe redox.This strategy provides a new pathway toward improving the stability and O redox reversibility of P3-type cathode materials for sodium-ion batteries.展开更多
materials,despite its intensive application in Li/Na-ion batteries.The existing mechanisms of AVE's effects mainly focus on charge transfer but fail to clarify other critical issues.Here,we propose a new insight i...materials,despite its intensive application in Li/Na-ion batteries.The existing mechanisms of AVE's effects mainly focus on charge transfer but fail to clarify other critical issues.Here,we propose a new insight into AVE's effect on K-ion storage by introducing Te vacancies into a representative conversion-type NiTe.In addition to existing mechanisms,we demonstrate Te vacancies play three other unprecedented roles.(1)Te vacancies minimize the intrinsic volume strain from 15%to 6%,significantly suppressing anode pulverization and element dissolution.(2)Te vacancies induce the in-situ formation of a thin yet robust KF-based inorganic-rich solid electrolyte interphase,further accommodating volume strain and element dissolution.(3)Te vacancies reduce Ni-Te bond lengths and promote K-ion diffusion by modulating local atomic structure.Therefore,NiTe_(1-x)delivers an outstanding cycling performance(229.5 mAh g1 at 3.0 A g^(-1)for 1350 cycles)and rate capability(171.7 mAh g^(-1)at 5.0 A g^(-1)1).Furthermore,NiTe_(1-x)-based full cells showcase a remarkable energy density of 200.4 Wh kg^(-1).This work comprehensively elucidates the AVE's effects on alkali-ion storage,promoting the development of advanced conversion-type anode materials for practical applications.展开更多
Persistently high arsenic levels in drinkingwater threaten underprivileged areas worldwide.Although nanomaterials exhibit exceptional arsenic removal properties,their implementation presents challenges.We converted N-...Persistently high arsenic levels in drinkingwater threaten underprivileged areas worldwide.Although nanomaterials exhibit exceptional arsenic removal properties,their implementation presents challenges.We converted N-methylimidazole-modified polyvinyl chloride into a granular anion exchange resin(PNAXRs)using an environmentally friendly and gentle synthesis method.Additionally,a unified approach for embedding nanomaterials within these resins was proposed,yielding a TiO_(2) composite resin(TiO_(2)@PNAXRs).Structural characterization confirmed the successful grafting of imidazolium cations with anion-exchange properties onto polyvinyl chloride side chains.BET analysis indicates a high specific surface area of 70.31 m^(2)/g for the PNAXRs.TGA curves demonstrate the successful encapsulation of approximately 24.9%TiO_(2) within the composite resin.The SEM-EDS results show a uniform distribution of TiO_(2) in the PNAXRs,which facilitates the effective utilization of TiO_(2).Adsorption experiments in conjunction with XPS analysis provided insights into the dual role of inner-sphere complexation and ion exchange in the adsorption mechanism of As(V)by TiO_(2)@PNAXRs.In dynamic adsorption tests utilizing high-As(V)groundwater from the Datong Basin as the influent,TiO_(2)@PNAXRs demonstrated the ability to produce effluents that meet the World Health Organization’s recommended limit for arsenic in drinking water,with a capacity of 1780 bed volumes.These findings support the use of PNAXRs as ideal matrices for TiO_(2) and their practical application in As(V)removal processes.展开更多
基金UKRI financial support under grant number EP/Y026098/1 for Global Hydrogen Production Technologies(HyPT)Center。
文摘Anion-exchange membrane water electrolysers(AEMWEs)and fuel cells(AEMFCs)are critical technologies for converting renewable resources into green hydrogen(H_(2)),where anion-exchange membranes(AEMs)play a vital role in efficiently transporting hydroxide ions(OH^(-))and minimizing fuel crossover,thus enhancing overall efficiency.While conventional AEMs with linear,side-chain,and block polymer architectures show promise through functionalization,their long-term performance remains a concern.To address this,hyperbranched polymers offer a promising alternative due to their three-dimensional structure,higher terminal functionality,and ease of functionalization.This unique architecture provides interconnected ion transport pathways,fractional free volume,and enhanced long-term stability in alkaline environments.Recent studies have achieved conductivities as high as 304.5 mS cm^(-1),attributed to their improved fractional free volume and microphase separation in hyperbranched AEMs.This review explores the chemical,mechanical,and ionic properties of hyperbranched AEMs in AEMFCs and assesses their potential for application in AEMWEs.Strategies such as blending and structural functionalisation have significantly improved the properties by promoting microphase separation and increasing the density of cationic groups on the polymer surface.The review provides essential insights for future research,highlighting the challenges and opportunities in developing high-performance hyperbranched AEMs to advance hydrogen energy infrastructure.
基金supported by the National Natural Science Foundation of China(22075196,U22A20418,21878204)the Research Project Supported by Shanxi Scholarship Council of China(2022-050).
文摘Transition metal-based compounds can serve as pre-catalysts to obtain genuine oxygen evolution reaction(OER)electrocatalysts in the form of oxyhydroxides through electrochemical activation.However,the role and existence form of leached oxygen anions are still controversial.Herein,we selected iron selenite-wrapped hydrated nickel molybdate(denoted as NiMoO/FeSeO)as a pre-catalyst to study the oxyanion effect.It is surprising to find that SeO_(2)-exists in the catalyst in the form of intercalation,which is different from previous studies that suggest that anions are doped with residual elements after electrochemical activation,or adsorbed on the catalyst surface.The experiment and theoretical calculations show that the existence of SeO_(4)^(2-)intercalation effectively adjusts the electronic structure of NiFeOOH,promotes intramolecular electron transfer and O-O release,and thus lowers the reaction energy barrier.As expected,the synthesized NiFeOOH-SeO only needs 202 and 285 mV to attain 100 and 1000 mA cm^(-2)in 1 M KOH.Further,the anion exchange membrane water electrolyzer(AEMWE)consisting of NiFeOOHSeO anode and Pt/C cathode can reach 1 A cm^(-2)at 1.70 V and no significant attenuation within 300 h.Our findings provide insights into the mechanism,by which the intercalated oxyanions enhance the OER performance of NiFeOOH,thereby facilitating large-scale hydrogen production through AEMWE.
文摘Oxygen evolution reaction(OER)is often regarded as a crucial bottleneck in the field of renewable energy storage and conversion.To further accelerate the sluggish kinetics of OER,a cation and anion modulation strategy is reported here,which has been proven to be effective in preparing highly active electrocatalyst.For example,the cobalt,sulfur,and phosphorus modulated nickel hydroxide(denoted as NiCoPSOH)only needs an overpotential of 232 mV to reach a current density of 20 mA cm^(–2),demonstrating excellent OER performances.The cation and anion modulation facilitates the generation of high-valent Ni species,which would activate the lattice oxygen and switch the OER reaction pathway from conventional adsorbate evolution mechanism to lattice oxygen mechanism(LOM),as evidenced by the results of electrochemical measurements,Raman spectroscopy and differential electrochemical mass spectrometry.The LOM pathway of NiCoPSOH is further verified by the theoretical calculations,including the upshift of O 2p band center,the weakened Ni–O bond and the lowest energy barrier of rate-limiting step.Thus,the anion and cation modulated catalyst NiCoPSOH could effectively accelerate the sluggish OER kinetics.Our work provides a new insight into the cation and anion modulation,and broadens the possibility for the rational design of highly active electrocatalysts.
基金supported by the National Natural Science Foundation of China,Nos.82172196(to KX),82372507(to KX)the Natural Science Foundation of Hunan Province,China,No.2023JJ40804(to QZ)the Key Laboratory of Emergency and Trauma(Hainan Medical University)of the Ministry of Education,China,No.KLET-202210(to QZ)。
文摘Ischemia–reperfusion injury is a common pathophysiological mechanism in retinal degeneration.PANoptosis is a newly defined integral form of regulated cell death that combines the key features of pyroptosis,apoptosis,and necroptosis.Oligomerization of mitochondrial voltage-dependent anion channel 1 is an important pathological event in regulating cell death in retinal ischemia–reperfusion injury.However,its role in PANoptosis remains largely unknown.In this study,we demonstrated that voltage-dependent anion channel 1 oligomerization-mediated mitochondrial dysfunction was associated with PANoptosis in retinal ischemia–reperfusion injury.Inhibition of voltage-dependent anion channel 1 oligomerization suppressed mitochondrial dysfunction and PANoptosis in retinal cells subjected to ischemia–reperfusion injury.Mechanistically,mitochondria-derived reactive oxygen species played a central role in the voltagedependent anion channel 1-mediated regulation of PANoptosis by promoting PANoptosome assembly.Moreover,inhibiting voltage-dependent anion channel 1 oligomerization protected against PANoptosis in the retinas of rats subjected to ischemia–reperfusion injury.Overall,our findings reveal the critical role of voltage-dependent anion channel 1 oligomerization in regulating PANoptosis in retinal ischemia–reperfusion injury,highlighting voltage-dependent anion channel 1 as a promising therapeutic target.
基金supported by the National Natural Science Foundation of China(22478422,22238012,and 22178384)Science Foundation of China University of Petroleum,Beijing(2462024QNXZ003)CHN Energy Investment Group(GJNY23-23)。
文摘Designing transition metal nickel-cobalt-based battery-type electrode materials driven by anions is crucial for achieving rapid OH-ion transport under electrochemical activation conditions,thereby improving capacitance performance.Herein,borate anions are selected through theoretical calculations,and twodimensional(2D)defect-rich amorphous nickel-cobalt-based borate is synthesized via a facile chemical reduction method.Under potentiostatic modification,activated products(NCB-G-E)are obtained.In situ Raman spectra reveal that electron-deficient borate extracts electrons from metal centers,facilitating the oxidation state transition of Ni and Co.Theoretical calculations show that in situ adsorbed borate regulates the d-band centers of metal sites,enhancing OH^(-)intermediate adsorption.Meanwhile,borate anion adsorption accelerates the deprotonation and activation processes.Electrochemical tests demonstrate that NCB-G-E displays superior capacitance performance,with a high quality specific capacity of383.3 mA h g^(-1)and 65% retention rate at 30 A g^(-1),surpassing most nickel-cobalt-based electrodes.The assembled asymmetric supercapacitor presents an impressive energy density of 68.2 Wh kg^(-1)and good cycling stability.This work highlights the role of electron-deficient borate in tuning metal band structure and promoting oxidation state transition through synergistic defect advantages,offering new prospects for advanced battery-type energy storage materials.
基金funding support from the National Science Fund for Distinguished Young Scholars(Grant No.T2225027)the National Natural Science Foundation of China(Grant Nos.12074013 and 12204419)the China Postdoctoral Science Foundation(Grant No.2021M702956)。
文摘Electrides,characterized by spatially confined anionic electrons,have emerged as a promising class of materials for catalysis,magnetism,and superconductivity.However,transition-metal-based electrides with diverse electron dimensionalities remain largely unexplored.Here,we perform a comprehensive first-principles investigation of Y-Co electrides,focusing on Y_(3)Co,Y_(3)Co_(2),and YCo.Our calculations reveal a striking dimensional evolution of anionic electrons:from two-dimensional(2D)confinement in YCo to one-dimensional(1D)in Y_(3)Co_(2)and zero-dimensional(0D)in Y_(3)Co.Remarkably,the YCo monolayer exhibits intrinsic ferromagnetism,with a magnetic moment of 0.65μB per formula unit arising from spin-polarized anionic electrons mediating long-range coupling between Y and Co ions.The monolayer also shows a low exfoliation energy(1.66 J/m^(2)),indicating experimental feasibility.All three electrides exhibit low work functions(2.76 eV-3.11 eV)along with Co-centered anionic states.This work expands the family of transition-metal-based electrides and highlights dimensionality engineering as a powerful strategy for tuning electronic and magnetic properties.
基金supported by National Key Research and Development Program of China(2022YFB2402200)the China Postdoctoral Science Foundation(grant nos.2023T160591)the Joint Fund of the Technical R&D Program of Henan Province(grant nos.232301420044).
文摘Electrolytes are crucial components in electrochemical energy storage devices,sparking considerable research interest.However,the significance of anions in the electrolytes is often underestimated.In fact,the anions have significant impacts on the performance and stability of lithium batteries.Therefore,comprehensively understanding anion chemistry in electrolytes is of crucial importance.Herein,indepth comprehension of anion chemistry and its positive effects on the interface,solvation structure of Li-ions,as well as the electrochemical performance of the batteries have been emphasized and summarized.This review aims to present a full scope of anion chemistry and furnish systematic cognition for the rational design of advanced electrolytes for better lithium batteries with high energy density,lifespan,and safety.Furthermore,insightful analysis and perspectives based on the current research are proposed.We hope that this review sheds light on new perspectives on understanding anion chemistry in electrolytes.
基金supported by the National Natural Science Foundation of China(Nos.52222317,21902144,52225208)the“Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang”(No.2020R01002)+1 种基金the Natural Science Foundation of Zhejiang Province(No.LZ23E020002)the Fundamental Research Funds for the Provincial Universities of Zhejiang(No.RFC2023002).
文摘Anion modification has been considered as a strategy to improve water splitting efficiency upon oxygen evolution reaction(OER).However,constructing a novel catalysis system with high catalytic activity and precise structures is still a huge challenge due to the tedious procedure of precursor synthesis and anion selection.Here,a bimetallic(FeNi)nanowire self-assembled superstructure was synthesized using the Hoffmann rearrangement method,and then functionalized with four anions(P,Se,S,and O).Notably,the Fe_(3)Se_(4)/Ni_(3)Se_(4) catalyst shows a high conductivity,enhances the adsorption of intermediate products,accelerates the rate-determining step,and consequently results to improved electrocatalytic performance.Using the Fe_(3)Se_(4)/Ni_(3)Se_(4) catalyst exhibits enhanced performance with overpotential of 316mV at 10 mA/cm^(2),in stark contrast to Fe_(2) P/Ni_(2)P(357mV),Fe_(7)S_(8)/NiS(379 mV),and Fe_(3)O_(4)/NiO(464 mV).Moreover,the formation mechanism of superstructure and the relationship between electronegativities and electrocatalytic properties,are elucidated.Accordingly,this work provides an efficient approach to Hoffmann-type coordination polymer catalyst for oxygen evolution towards a near future.
基金National Natural Science Foundation of China (52372224 and 52072299)Major Project of Shaanxi Coal Joint Fund of Shaanxi Provincial Science and Technology Department (2019JLZ-07)。
文摘Na_(3)V_(2)(PO_(4))_(2)O_(2)F (VP) is recognized as a promising cathode material for sodium-ion batteries due to its stable structural framework and high specific capacity.Density functional theory (DFT) and finite element simulations show that incorporating SO_(4)^(2-)into VP decreases its band gap,lowers the migration energy barrier,and ensures a uniform Na+concentration gradient and stress distribution during charge and discharge cycles.Consequently,the average Na+diffusion coefficient of Na_(3)V_(2)(PO_(4))_(1.95)(SO_(4))_(0.05)O_(2)F(VPS-1) is roughly double that of VP,leading to enhanced rate capability (80 C,75.5 mAh g^(-1)) and cycling stability (111.0 mAh g^(-1)capacity after 1000 cycles at 10 C current density) for VPS-1.VPS-1 exhibits outstanding fast-charging capabilities,achieving an 80%state of charge in just 8.1 min.The assembled VPS-1//SbSn/NPC full cell demonstrated stable cycling over 200 cycles at a high 5 C current,maintaining an average coulombic efficiency of 95.35%.
基金supported by the Research Fund of Jianghan Univer-sity(2024JCYJ02)the Graduate Scientific Research Foundation of Jianghan University(KYCXJJ202428)+1 种基金the Excellent Discipline Cultiva-tion Project funded by Jianghan University(2023XKZ013)the Na-tional Natural Science Foundation of China(Grant No.22179052).
文摘Lithium (Li) metal batteries (LMBs) featuring ultrahigh energy densities are expected as ones of the mostprominent devices for future energy storage applications. Nevertheless, the practical application of LMBs is stillplagued by the poor interfacial stability of Li metal anode. Inorganic-rich interlayer derived from anion decom-positionin advanced liquid electrolytes is demonstrated as an efficient approach to stabilize the Li metal anode,however, is electrolyte-dependent with limited application conditions due to inappropriate electrolyte properties.Herein, an efficient structuration strategy is proposed to fabricate an electrolyte-independent and sustainedinorganic-rich layer, by embedding a type of functional anion aggregates consisting of selected anions ionicallybonded to polymerized cation clusters. The anion aggregates can progressively release anions to react with Liþand form key components boosting the structural stability and Liþ transfer ability of the artificial layer uponcycling. This self-reinforcing working mechanism endows the artificial layer with a sustained inorganic-richnature and promising Li protective ability during long-term cycling, while the electrolyte-independent propertyenables its applications in LMBs using conventional low concentration electrolytes and all-solid-state LMBs withsignificantly enhanced performances. This strategy establishes an alternative designing route of Li protectivelayers for reliable LMBs.
基金financially supported by the National Natural Science Foundation of China(52202228,52402298)Science Research Project of Hebei Education Department(BJK2022011)+3 种基金Central Funds Guiding the Local Science and Technology Development of Hebei Province(236Z4404G)Beijing Tianjin Hebei Basic Research Cooperation Special Project(E2024202273)Science and Technology Correspondent Project of Tianjin(24YDTPJC00240)supported by the U.S.Department of Energy’s Office of Science,Office of Basic Energy Science,Materials Sciences and Engineering Division。
文摘The poor electrode/electrolyte interface compatibility and inferior electrolyte oxidative tolerance in commercial ethylene carbonate(EC)-based electrolytes have hindered the development of high-voltage sodium-ion batteries(SIBs).In this study,an anionic chemistry strategy is proposed to strengthen Na^(+)-anion coordination in the solvation sheath,and subsequently reduce the coordination numbers of EC solvents with the addition of NaClO_(4)into NaPF_(6)/EC/DEC electrolytes.Theoretical and experimental results confirm that the competitive coordination capabilities of Na^(+)-ClO_(4)^(-),with high binding energy,induce a wide electrochemical window up to 4.8 V,highly reversible Na^(+)plating/stripping,and fast desolvation kinetics at the electrode/electrolyte interface,thereby hindering the continuous electrolyte decomposition.The optimized electrolyte PEDCF-0.20 demonstrates weakened Na^(+)-EC coordination,increased interaction of Na^(+)-anion in solvation,facilitating the formation of an inorganic-rich interface layer.Consequently,a 2.1 A h cylindrical full cell of hard carbon//NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)delivers an impressive capacity retention of 93.7% after 300 cycles at an extended charging cutoff voltage of 4.1 V.This work provides a new insight into regulating the competitive coordination of anions to guarantee the remarkable cycling stability of high-voltage SIBs.
基金supported by the National Natural Science Foundation of China(Grant No.52403305)the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDB0880000)+1 种基金Tianchi Talent Program of Xinjiang Uygur Autonomous Region(Grant No.2024000068)Postdoctoral Fellow-ship Program(Grade C)(Grant No.GZC20232959)。
文摘The prediction of new fluorooxoborates as ultraviolet(UV)/deep ultraviolet(DUV)opto-electronic functional materials from a largely unexplored chemical space is a challenging task.It has been suggested that the anionic frameworks formed by B–O and B–O–F units significantly determine the physical properties of fluorooxoborates.Therefore,the rational design of anionic frameworks could facilitate the materials discovery process.Herein,we propose that a candidate anionic framework can be efficiently derived from an existing one by slightly altering its oxygen content.Following this idea,we hypothesized the existence of a 1D[B_(3)O_(5)F]_(∞)chain from the wellknown 2D[B_(6)O_(9)F_(2_)]_(∞)layer.Accordingly,seven CaB_(3)O_(5)F structures with the expected anionic framework were successfully predicted.First-principles calculations show that all these structures have potential in the UV/DUV birefringent or nonlinear optical(NLO)material field,indicating that the 1D[B_(3)O_(5)F]_(∞)chain is indeed a promising anionic framework for achieving UV/DUV birefringent and NLO performance.
基金National Key Research and Development Program of China,Grant/Award Number:2022YFB2502000National Natural Science Foundation of China,Grant/Award Number:52207244。
文摘In the realm of sodium-ion batteries(SIBs),Mn-based layered oxide cathodes have garnered considerable attention owing to their anionic redox reactions(ARRs).Compared to other types of popular sodium-ion cathodes,Mn-based layered oxide cathodes with ARRs exhibit outstanding specific capacity and energy density,making them promising for SIB applications.However,these cathodes still face some scientific challenges that need to be addressed.This review systematically summarizes the composition,structure,oxygen-redox mechanism,and performance of various types of Mn-based cathodes with ARRs,as well as the main scientific challenges they face,including sluggish ion diffusion,cationic migration,O_(2) release,and element dissolution.Currently,to resolve these challenges,efforts mainly focus on six aspects:synthesis methods,structural design,doped modification,electrolyte design,and surface engineering.Finally,this review provides new insights for future direction,encompassing both fundamental research,such as novel cathode types,interface optimization,and interdisciplinary research,and considerations from an industrialization perspective,including scalability,stability,and safety.
基金supported by the National Natural Science Foundation of China(No.52301260)the National Science Foundation of Jiangsu Province(No.BK20230712)China Postdoctoral Science Foundation(No.2022M711686).
文摘The two-dimensional MoSe_(2)possesses a large interlayer spacing(0.65 nm)and a narrow bandgap(1.1 eV),showing potential in sodium-ion storage.However,it faces slow kinetics and volume stress during Na^(+)(de)intercalation process,thereby affecting the cycling stability and lifespan of sodium-ion batteries(SIBs).In this work,a novel approach involving anionic doping and structural design has been proposed,wherein a two-step in-situ selenization and surface thermal annealing doping process is applied to fabricate a novel configuration material of fluorine-doped MoSe_(2)@nitrogen-doped carbon nanosheets(F-MoSe_(2)@FNC).The obtained F-MoSe_(2)@FNC,benefiting from the dual advantages of structure and F-doping,synergistically promotes and accelerates the stable(de)intercalation of Na^(+).Henceforth,F-MoSe_(2)@FNC demonstrates notable characteristics in terms of reversible specific capacity,boasting a high initial coulombic efficiency of 76.97%,alongside remarkable rate capabilities and cyclic stability.The constructed F-MoSe_(2)@FNC anode-based half cell manifests exceptional longevity,enduring up to 2550 cycles at 10 A·g^(-1)with a specific capacity of 322.04 mAh·g^(-1).Its electrochemical performance surpasses that of MoSe_(2)@NC and Pure MoSe_(2),underscoring the significance of the proposed synergistic modulation.Through comprehensive kinetic analyses,encompassing in-situ electrochemical impedance spectroscopy(EIS),it is elucidated that the F-MoSe_(2)@FNC electrode showcases elevated pseudo-capacitance and rapid diffusion attributes during charge and discharge processes.Furthermore,the assembled full-cell(F-MoSe_(2)@FNC//Na_(3)V_(2)(PO_(4))_(3))attains a notable energy density of 166.94 Wh·kg^(-1).This design provides insights for the optimization of MoSe_(2)electrodes and their applications in SIBs.
基金funding programs,the Walter Benjamin Programme(DFG,German Research Foundation,project number:530742479)the ProChancecareer Programme for the Promotion of Equal Opportunities in Academia for providing the financial support+1 种基金financial support by the Deutsche Forschungsgemeinschaft via the TRR 234 Cata Light(DFG,German Research Foundation)-Projektnummer 364549901-TRR 234[B6]the financial support taken from the CSIR and UGC,Delhi,India。
文摘The photocatalytic reduction of CO_(2)is a crucial area of research aimed at addressing the dual challenges of mitigating rising CO_(2)emissions and producing sustainable chemical feedstocks.While multielectron reduction pathways for CO_(2)are well explored,the single electron reduction to produce the highly reactive carbon dioxide radical anion(CO_(2)^(·-))remains challenging yet promising for green organic transformations.This review contributes to the field by providing a comprehensive analysis of the mechanisms,materials,and reaction pathways involved in CO_(2)^(·-)generation,focusing on the use of visible-lightdriven photocatalytic materials to circumvent the need for high-energy ultraviolet irradiation.Through a systematic examination of CO_(2)^(·-)production,detection methods,and chemical utilization in photocatalytic carboxylation reactions,this review advances understanding of the chemistry of CO_(2)^(·-)and its applications in sustainable chemical synthesis.In addition,it highlights existing key challenges,such as redox potential limitations,and proposes strategies for scaling up photocatalytic systems to enable practical application.By illuminating the pathway to effectively photocatalyze CO_(2)^(·-)generation and its transformative potential in sustainable chemical synthesis,this review equips scientists with critical insights and strategic approaches for overcoming current limitations,driving innovation in photocatalytic materials for solar-to-chemical energy conversion.
基金supported by the National Key Research and Development Program (2019YFA0405601)National Science Foundation of China(No. 22309097, 22179066, 21902179)+1 种基金Shandong Provincial Natural Science Foundation (2023KJ228, ZR2021QE061, ZR202103010205)the Startup Foundation for Advanced Talents in Qingdao University (DC2000005106)
文摘Anionic redox reaction(ARR)can provide extra capacity beyond transition metal(TM)redox in lithium-rich TM oxide cathodes.Practical ARR application is much hindered by the structure instability,particularly at the surface.Oxygen release has been widely accepted as the ringleader of surficial structure instability.However,the role of TM in surface stability has been much overlooked,not to mention its interplay with oxygen release.Herein,TM dissolution and oxygen release are comparatively investigated in Li_(1.2)Ni_(0.2)Mn_(0.6)O_(2).Ni is verified to detach from the lattice counter-intuitively despite the overwhelming stoichiometry of Mn,facilitating subsequent oxygen release of the ARR process.Intriguingly,surface reorganization occurs following regulated Ni dissolution,enabling the stabilization of the surface and elimination of oxygen release in turn.Accordingly,a novel optimization strategy is proposed by adding a relaxation step at 4.50 V within the first cycle procedure.Battery performance can be effectively improved,with voltage decay suppressed from 3.44 mV/cycle to 1.60 mV/cycle,and cycle stability improved from 66.77%to 90.01%after 100 cycles.This work provides new perspectives for clarifying ARR surface instability and guidance for optimizing ARR performance.
基金supported by the National Key Scientific Research Project(No.2022YFB2502300)the National Natural Science Foundation of China(No.52071085).
文摘P3-type manganese-iron-based cathodes with high specific capacity and abundant resource have attracted considerable attention for sodium-ion batteries.However,the long-term cycle stability of P3-type cathodes is still not satisfactory.In this work,we design a new quaternary manganese-iron-based cathode material(P3-Na_(0.54)Mn_(0.64)Fe_(_(0.1)6)Mg_(0.1)Cu_(0.1)O_(2))by Cu substitution.The strong covalent Cu-O bonds improve the structural stability and the reversibility of O redox during charge and discharge processes.Cu substitution also mitigates the structure change with less unit cell volume variation,and improves the Na-ion transport kinetics effectively.As a result,NMFMC delivers much improved cycling stability and rate capability compared with NMFM.It reveals that the charge compensation of NMFMC is mainly contributed by Mn^(3+/4+),Fe^(3+/3.5+)and O_(2-/-)during the charge and discharge processes,and Cu substitution can also enhance the activity and reversibility of Fe redox.This strategy provides a new pathway toward improving the stability and O redox reversibility of P3-type cathode materials for sodium-ion batteries.
基金support from the National Natural Science Foundation of China(No.U23A20574,52201242)the Natural Science Foundation of Jiangsu Province(No.BK20240179).
文摘materials,despite its intensive application in Li/Na-ion batteries.The existing mechanisms of AVE's effects mainly focus on charge transfer but fail to clarify other critical issues.Here,we propose a new insight into AVE's effect on K-ion storage by introducing Te vacancies into a representative conversion-type NiTe.In addition to existing mechanisms,we demonstrate Te vacancies play three other unprecedented roles.(1)Te vacancies minimize the intrinsic volume strain from 15%to 6%,significantly suppressing anode pulverization and element dissolution.(2)Te vacancies induce the in-situ formation of a thin yet robust KF-based inorganic-rich solid electrolyte interphase,further accommodating volume strain and element dissolution.(3)Te vacancies reduce Ni-Te bond lengths and promote K-ion diffusion by modulating local atomic structure.Therefore,NiTe_(1-x)delivers an outstanding cycling performance(229.5 mAh g1 at 3.0 A g^(-1)for 1350 cycles)and rate capability(171.7 mAh g^(-1)at 5.0 A g^(-1)1).Furthermore,NiTe_(1-x)-based full cells showcase a remarkable energy density of 200.4 Wh kg^(-1).This work comprehensively elucidates the AVE's effects on alkali-ion storage,promoting the development of advanced conversion-type anode materials for practical applications.
基金supported by the Key Research and Development Plan of Zhejiang Province(No.2021C03176)the National Key Research and Development Program of China(No.2022YFC3703700).
文摘Persistently high arsenic levels in drinkingwater threaten underprivileged areas worldwide.Although nanomaterials exhibit exceptional arsenic removal properties,their implementation presents challenges.We converted N-methylimidazole-modified polyvinyl chloride into a granular anion exchange resin(PNAXRs)using an environmentally friendly and gentle synthesis method.Additionally,a unified approach for embedding nanomaterials within these resins was proposed,yielding a TiO_(2) composite resin(TiO_(2)@PNAXRs).Structural characterization confirmed the successful grafting of imidazolium cations with anion-exchange properties onto polyvinyl chloride side chains.BET analysis indicates a high specific surface area of 70.31 m^(2)/g for the PNAXRs.TGA curves demonstrate the successful encapsulation of approximately 24.9%TiO_(2) within the composite resin.The SEM-EDS results show a uniform distribution of TiO_(2) in the PNAXRs,which facilitates the effective utilization of TiO_(2).Adsorption experiments in conjunction with XPS analysis provided insights into the dual role of inner-sphere complexation and ion exchange in the adsorption mechanism of As(V)by TiO_(2)@PNAXRs.In dynamic adsorption tests utilizing high-As(V)groundwater from the Datong Basin as the influent,TiO_(2)@PNAXRs demonstrated the ability to produce effluents that meet the World Health Organization’s recommended limit for arsenic in drinking water,with a capacity of 1780 bed volumes.These findings support the use of PNAXRs as ideal matrices for TiO_(2) and their practical application in As(V)removal processes.
