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
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
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
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
The rapidly growing electric cars and energy storage systems have extremely promoted the development of advanced lithium and sodium ion batteries and stimulated evolution of high-capacity cathodes.Li/Na-rich layered c...The rapidly growing electric cars and energy storage systems have extremely promoted the development of advanced lithium and sodium ion batteries and stimulated evolution of high-capacity cathodes.Li/Na-rich layered cathodes consisting cationic and anionic reactions as the most typical representative of high-capacity cathodes have shown its tremendous potential.However,there is a long way to go before commercialization because of unsatisfactory performances including large voltage hysteresis,voltage fade and poor cycle performance.Numerous investigations on redox mechanisms and engineering strategies have been performed from the point view of structure and made significant progress,which has been well reviewed.Meanwhile,the unacceptable issues are essentially correlated to the electronic configuration of anionic redox and its interaction with adjacent transition metal cations,which can be well depicted from electronic structure.However,the investigations on anionic reaction process in the viewpoint of electronic structure have been much less summarized.This review aims to compile the current knowledge of anionic redox from the point view of electronic structure,including configuration,origination,evolution,detection and coupling relationship with cationic redox.This work is attempted to inspire new perspectives and design approaches for the development of high-capacity cathodes.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
Aqueous zinc ion batteries(AZIBs)have excellent development prospects due to their high theoretical capacity and low cost.Nevertheless,the commercial separator represented by glass fiber(GF)in AZIBs usually exhibits u...Aqueous zinc ion batteries(AZIBs)have excellent development prospects due to their high theoretical capacity and low cost.Nevertheless,the commercial separator represented by glass fiber(GF)in AZIBs usually exhibits uneven porosity,poor zincophilicity,and insufficient functional groups,resulting in the emergence of the zinc anode dendrites and side reactions.Designing a separator with specific interfacial ion transport behavior is essential to achieve a highly stable reversible zinc anode.Herein,an anionic metal-organic framework(MOF)functionalized separator(GF-Bio-MOF-100)was presented to accelerate the desolvation process and modulate Zn^(2+)flux,thereby delivering the decreased nucleation overpotential and uniform Zn^(2+)deposition.The in-depth kinetics investigations combined with the in-situ Raman spectroscopy demonstrate that the carbonyl group within the Bio-MOF-100 is capable of capturing the H_(2)O molecules of[Zn(H_(2)O)_(6)]^(2+)via the H-bond interaction,which further accelerates the desolvation process and transport kinetics of Zn^(2+).Meanwhile,the anionic framework of the GFBio-MOF-100 separator acts as an interfacial ion channel to regulate the Zn^(2+)flux and enables dendrite-free Zn^(2+)deposition and growth.Consequently,the Zn|GF-Bio-MOF-100|Zn symmetric cell exhibited a stable Zn^(2+)plating/stripping behavior and it could cycle for 2000 h at 0.3 mA cm^(-2).Additionally,the assembled Zn|GF-Bio-MOF-100|MnO_(2)full cell delivers a capacity retention of 83.9% after 1000 cycles at 0.5 A g^(-1).This work provides new insights into the design of functionalized separators for long-life AZIBs.展开更多
Lithium-rich layered oxides (LLOs) are increasingly recognized as promising cathode materials for nextgeneration high-energy-density lithium-ion batteries (LIBs).However,they suffer from voltage decay and low initial ...Lithium-rich layered oxides (LLOs) are increasingly recognized as promising cathode materials for nextgeneration high-energy-density lithium-ion batteries (LIBs).However,they suffer from voltage decay and low initial Coulombic efficiency (ICE) due to severe structural degradation caused by irreversible O release.Herein,we introduce a three-in-one strategy of increasing Ni and Mn content,along with Li/Ni disordering and TM–O covalency regulation to boost cationic and anionic redox activity simultaneously and thus enhance the electrochemical activity of LLOs.The target material,Li_(1.2)Ni_(0.168)Mn_(0.558)Co_(0.074)O_(2)(L1),exhibits an improved ICE of 87.2%and specific capacity of 293.2 mA h g^(-1)and minimal voltage decay of less than 0.53 m V cycle-1over 300 cycles at 1C,compared to Li_(1.2)Ni_(0.13)Mn_(0.54)Co_(0.13)O_(2)(Ls)(274.4 mA h g^(-1)for initial capacity,73.8%for ICE and voltage decay of 0.84 mV/cycle over 300 cycles at 1C).Theoretical calculations reveal that the density of states (DOS) area near the Fermi energy level for L1 is larger than that of Ls,indicating higher anionic and cationic redox reactivity than Ls.Moreover,L1 exhibits increased O-vacancy formation energy due to higher Li/Ni disordering of 4.76%(quantified by X-ray diffraction Rietveld refinement) and enhanced TM–O covalency,making lattice O release more difficult and thus improving electrochemical stability.The increased Li/Ni disordering also leads to more Ni^(2+)presence in the Li layer,which acts as a pillar during Li+de-embedding,improving structural stability.This research not only presents a viable approach to designing low-Co LLOs with enhanced capacity and ICE but also contributes significantly to the fundamental understanding of structural regulation in high-performance LIB cathodes.展开更多
Emulsification is one of the important mechanisms of surfactant flooding. To improve oil recovery for low permeability reservoirs, a highly efficient emulsification oil flooding system consisting of anionic surfactant...Emulsification is one of the important mechanisms of surfactant flooding. To improve oil recovery for low permeability reservoirs, a highly efficient emulsification oil flooding system consisting of anionic surfactant sodium alkyl glucosyl hydroxypropyl sulfonate(APGSHS) and zwitterionic surfactant octadecyl betaine(BS-18) is proposed. The performance of APGSHS/BS-18 mixed surfactant system was evaluated in terms of interfacial tension, emulsification capability, emulsion size and distribution, wettability alteration, temperature-resistance and salt-resistance. The emulsification speed was used to evaluate the emulsification ability of surfactant systems, and the results show that mixed surfactant systems can completely emulsify the crude oil into emulsions droplets even under low energy conditions. Meanwhile,the system exhibits good temperature and salt resistance. Finally, the best oil recovery of 25.45% is achieved for low permeability core by the mixed surfactant system with a total concentration of 0.3 wt%while the molar ratio of APGSHS:BS-18 is 4:6. The current study indicates that the anionic/zwitterionic mixed surfactant system can improve the oil flooding efficiency and is potential candidate for application in low permeability reservoirs.展开更多
Nitroaromatic hydrogenation catalysis without precious metals remains a longstanding challenge.The rate of electron transfer is the crucial factor affecting hydrogenation catalysis.Herein,an ionic Cd-based metal-organ...Nitroaromatic hydrogenation catalysis without precious metals remains a longstanding challenge.The rate of electron transfer is the crucial factor affecting hydrogenation catalysis.Herein,an ionic Cd-based metal-organic framework(I-Cd-MOF)exhibiting a unique structure with one-dimensional(1D)opening nanochannels and good electron transfer ability was synthesized for catalyzing hydrogenation of 4-nitrophenol(4-NP).The catalytic activity of the unique I-Cd-MOF without noble metals is detected,which is higher than most reported noble metal catalysts.Remarkably,the reaction rate of I-Cd-MOF(4.28 min^(-1))is about 47.6 times higher than that of the Cd-based neutral MOF(N-Cd-MOF)with the similar crystalline structure.Liquid chromatograph mass spectrometer(LC-MS)and theoretical results demonstrate that 4-NP and five intermediates are stabilized in the channels of I-Cd-MOF,which increases the possibility of contact with H^*and H_(2)g enerated at the Cd sites.The I-Cd-MOF was extended to other nitroaromatic hydrogenation catalysis,which still displays excellent activity.More importantly,the I-MOF@Filter membrane was successfully constructed for continuous hydrogenation catalytic reactions,which maintains a high catalytic performance after 7 cycles of recycling without washing.This work fills in the application of the I-MOFs in hydrogenation catalytic reactions and provides an effective way for the rapid and green degradation of nitroaromatic compounds.展开更多
For living anionic polymerization(LAP),solvent has a great influence on both reaction mechanism and kinetics.In this work,by using the classical butyl lithium-styrene polymerization as a model system,the effect of sol...For living anionic polymerization(LAP),solvent has a great influence on both reaction mechanism and kinetics.In this work,by using the classical butyl lithium-styrene polymerization as a model system,the effect of solvent on the mechanism and kinetics of LAP was revealed through a strategy combining density functional theory(DFT)calculations and kinetic modeling.In terms of mechanism,it is found that the stronger the solvent polarity,the more electrons transfer from initiator to solvent through detailed energy decomposition analysis of electrostatic interactions between initiator and solvent molecules.Furthermore,we also found that the stronger the solvent polarity,the higher the monomer initiation energy barrier and the smaller the initiation rate coefficient.Counterintuitively,initiation is more favorable at lower temperatures based on the calculated results ofΔG_(TS).Finally,the kinetic characteristics in different solvents were further examined by kinetic modeling.It is found that in benzene and n-pentane,the polymerization rate exhibits first-order kinetics.While,slow initiation and fast propagation were observed in tetrahydrofuran(THF)due to the slow free ion formation rate,leading to a deviation from first-order kinetics.展开更多
Renewable energy conversion as well as water electrolysis technologies are constrained by the fact that kinetics are always slow in the electrocatalytic oxygen evolution reaction(OER).There are numerous means and stra...Renewable energy conversion as well as water electrolysis technologies are constrained by the fact that kinetics are always slow in the electrocatalytic oxygen evolution reaction(OER).There are numerous means and strategies for the enhancement of OER activity.In this paper,we systematically review the important role of anionic vacancies in enhancing the OER activity of catalysts:increasing catalyst conductivity,improving electrical conductivity,and enhancing intermediate adsorption.In order to better detect the presence of vacancies in the samples,the principle of vacancy detection is reviewed in detail in terms of both spectroscopic and microscopic characterization,and the methods of vacancy formation as well as the factors influencing the concentration of vacancies are summarized in detail.In addition,the challenges and new directions for the study of anionic vacancies are provided.Lei Wang was awarded a Ph.D.in chemistry from Jilin University in 2006 under the supervision of Prof.Shouhua Feng.He worked as a Postdoctoral Scholar in Shandong University,the State Key Laboratory of Crystal Materials from 2008 to 2010.He is currently a professor at Qingdao University of Science and Technology.His research interests mainly focus on the design and synthesis of functional organic-inorganic hybrids and porous MOFs materials,as well as their applications in photocatalysis,electrocatalysis,lithium-ion battery,etc.Jingqi Chi received her B.S.degree and Ph.D.degree from the State Key Laboratory of Heavy Oil Processing,China University of Petroleum(East China).She is currently an associate professor at Qing dao University of Science and Technology.Her research interests focus on the design and synthesis of transition metal-based nanostructures and porous MOFs materials for electrochemical applications.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
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
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
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
A plasma injection ion source has been de-veloped for the photoelectron velocity imag-ing studies of metal-containing anions.The source employs a pulse discharge nozzle for generating a plasma beam that perpendicu-lar...A plasma injection ion source has been de-veloped for the photoelectron velocity imag-ing studies of metal-containing anions.The source employs a pulse discharge nozzle for generating a plasma beam that perpendicu-larly crosses the master supersonic jet beam from a home-made pulsed piezo valve.The discharge nozzle is designed for high voltage gas discharge with efficient metal sputtering of the cathode,and thus plays a role in met-al atom and ion source.Supersonically jet-cooled anions can be produced in the master gas jet via reactions of the plasma products.The source is integrated into a photoelectron ve-locity imaging spectrometer.Test mass spectrometry experiments show that the ion source can efficiently produce transition metal containing anions,such as FeO_(m)^(-),CuO_(m)^(-),CuC_(n)^(-),CuC_(n)O_(m)^(-).The photoelectron imaging results by photodetachment of O-show that the pho-toelectron energy resolution of the whole instrument isΔE/E≈2.3%,and the results of FeO^(-)indicate that internal temperatures of anions from the source could be efficiently cooled down.展开更多
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financially supported by the National Key Research and Development Program of China(No.2019YFA0405601)the National Natural Science Foundation of China(No.52130202)the Scientific Research Foundation for High-level Talents of Anhui University of Science and Technology(No.2022yjrc105)。
文摘The rapidly growing electric cars and energy storage systems have extremely promoted the development of advanced lithium and sodium ion batteries and stimulated evolution of high-capacity cathodes.Li/Na-rich layered cathodes consisting cationic and anionic reactions as the most typical representative of high-capacity cathodes have shown its tremendous potential.However,there is a long way to go before commercialization because of unsatisfactory performances including large voltage hysteresis,voltage fade and poor cycle performance.Numerous investigations on redox mechanisms and engineering strategies have been performed from the point view of structure and made significant progress,which has been well reviewed.Meanwhile,the unacceptable issues are essentially correlated to the electronic configuration of anionic redox and its interaction with adjacent transition metal cations,which can be well depicted from electronic structure.However,the investigations on anionic reaction process in the viewpoint of electronic structure have been much less summarized.This review aims to compile the current knowledge of anionic redox from the point view of electronic structure,including configuration,origination,evolution,detection and coupling relationship with cationic redox.This work is attempted to inspire new perspectives and design approaches for the development of high-capacity cathodes.
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supported by the National Natural Science Foundation of China(No.22278328)the Key Research and Development Program of Shaanxi Province(No.2023-YBGY-292)。
文摘Aqueous zinc ion batteries(AZIBs)have excellent development prospects due to their high theoretical capacity and low cost.Nevertheless,the commercial separator represented by glass fiber(GF)in AZIBs usually exhibits uneven porosity,poor zincophilicity,and insufficient functional groups,resulting in the emergence of the zinc anode dendrites and side reactions.Designing a separator with specific interfacial ion transport behavior is essential to achieve a highly stable reversible zinc anode.Herein,an anionic metal-organic framework(MOF)functionalized separator(GF-Bio-MOF-100)was presented to accelerate the desolvation process and modulate Zn^(2+)flux,thereby delivering the decreased nucleation overpotential and uniform Zn^(2+)deposition.The in-depth kinetics investigations combined with the in-situ Raman spectroscopy demonstrate that the carbonyl group within the Bio-MOF-100 is capable of capturing the H_(2)O molecules of[Zn(H_(2)O)_(6)]^(2+)via the H-bond interaction,which further accelerates the desolvation process and transport kinetics of Zn^(2+).Meanwhile,the anionic framework of the GFBio-MOF-100 separator acts as an interfacial ion channel to regulate the Zn^(2+)flux and enables dendrite-free Zn^(2+)deposition and growth.Consequently,the Zn|GF-Bio-MOF-100|Zn symmetric cell exhibited a stable Zn^(2+)plating/stripping behavior and it could cycle for 2000 h at 0.3 mA cm^(-2).Additionally,the assembled Zn|GF-Bio-MOF-100|MnO_(2)full cell delivers a capacity retention of 83.9% after 1000 cycles at 0.5 A g^(-1).This work provides new insights into the design of functionalized separators for long-life AZIBs.
基金National Natural Science Foundation of China (No.52202046)Natural Science Foundation of Shaanxi Province (No.2021JQ-034)。
文摘Lithium-rich layered oxides (LLOs) are increasingly recognized as promising cathode materials for nextgeneration high-energy-density lithium-ion batteries (LIBs).However,they suffer from voltage decay and low initial Coulombic efficiency (ICE) due to severe structural degradation caused by irreversible O release.Herein,we introduce a three-in-one strategy of increasing Ni and Mn content,along with Li/Ni disordering and TM–O covalency regulation to boost cationic and anionic redox activity simultaneously and thus enhance the electrochemical activity of LLOs.The target material,Li_(1.2)Ni_(0.168)Mn_(0.558)Co_(0.074)O_(2)(L1),exhibits an improved ICE of 87.2%and specific capacity of 293.2 mA h g^(-1)and minimal voltage decay of less than 0.53 m V cycle-1over 300 cycles at 1C,compared to Li_(1.2)Ni_(0.13)Mn_(0.54)Co_(0.13)O_(2)(Ls)(274.4 mA h g^(-1)for initial capacity,73.8%for ICE and voltage decay of 0.84 mV/cycle over 300 cycles at 1C).Theoretical calculations reveal that the density of states (DOS) area near the Fermi energy level for L1 is larger than that of Ls,indicating higher anionic and cationic redox reactivity than Ls.Moreover,L1 exhibits increased O-vacancy formation energy due to higher Li/Ni disordering of 4.76%(quantified by X-ray diffraction Rietveld refinement) and enhanced TM–O covalency,making lattice O release more difficult and thus improving electrochemical stability.The increased Li/Ni disordering also leads to more Ni^(2+)presence in the Li layer,which acts as a pillar during Li+de-embedding,improving structural stability.This research not only presents a viable approach to designing low-Co LLOs with enhanced capacity and ICE but also contributes significantly to the fundamental understanding of structural regulation in high-performance LIB cathodes.
基金financially supported by National Natural Science Foundation of China(No.22302229)Beijing Municipal Excellent Talent Training Funds Youth Advanced Individual Project(No.2018000020124G163)。
文摘Emulsification is one of the important mechanisms of surfactant flooding. To improve oil recovery for low permeability reservoirs, a highly efficient emulsification oil flooding system consisting of anionic surfactant sodium alkyl glucosyl hydroxypropyl sulfonate(APGSHS) and zwitterionic surfactant octadecyl betaine(BS-18) is proposed. The performance of APGSHS/BS-18 mixed surfactant system was evaluated in terms of interfacial tension, emulsification capability, emulsion size and distribution, wettability alteration, temperature-resistance and salt-resistance. The emulsification speed was used to evaluate the emulsification ability of surfactant systems, and the results show that mixed surfactant systems can completely emulsify the crude oil into emulsions droplets even under low energy conditions. Meanwhile,the system exhibits good temperature and salt resistance. Finally, the best oil recovery of 25.45% is achieved for low permeability core by the mixed surfactant system with a total concentration of 0.3 wt%while the molar ratio of APGSHS:BS-18 is 4:6. The current study indicates that the anionic/zwitterionic mixed surfactant system can improve the oil flooding efficiency and is potential candidate for application in low permeability reservoirs.
基金the financial support provided by the NSFC(No.21531007)the Shaanxi Provincial Natural Science Basic Research Program(No.2019JM-590)the Shaanxi Science and Technology Department(Nos.2022GY-384,2022JBGS2–07,2021LLRH05–21,2022QFY06–06)。
文摘Nitroaromatic hydrogenation catalysis without precious metals remains a longstanding challenge.The rate of electron transfer is the crucial factor affecting hydrogenation catalysis.Herein,an ionic Cd-based metal-organic framework(I-Cd-MOF)exhibiting a unique structure with one-dimensional(1D)opening nanochannels and good electron transfer ability was synthesized for catalyzing hydrogenation of 4-nitrophenol(4-NP).The catalytic activity of the unique I-Cd-MOF without noble metals is detected,which is higher than most reported noble metal catalysts.Remarkably,the reaction rate of I-Cd-MOF(4.28 min^(-1))is about 47.6 times higher than that of the Cd-based neutral MOF(N-Cd-MOF)with the similar crystalline structure.Liquid chromatograph mass spectrometer(LC-MS)and theoretical results demonstrate that 4-NP and five intermediates are stabilized in the channels of I-Cd-MOF,which increases the possibility of contact with H^*and H_(2)g enerated at the Cd sites.The I-Cd-MOF was extended to other nitroaromatic hydrogenation catalysis,which still displays excellent activity.More importantly,the I-MOF@Filter membrane was successfully constructed for continuous hydrogenation catalytic reactions,which maintains a high catalytic performance after 7 cycles of recycling without washing.This work fills in the application of the I-MOFs in hydrogenation catalytic reactions and provides an effective way for the rapid and green degradation of nitroaromatic compounds.
基金financially supported by the National Natural Science Foundation of China(U21A20313,22222807)。
文摘For living anionic polymerization(LAP),solvent has a great influence on both reaction mechanism and kinetics.In this work,by using the classical butyl lithium-styrene polymerization as a model system,the effect of solvent on the mechanism and kinetics of LAP was revealed through a strategy combining density functional theory(DFT)calculations and kinetic modeling.In terms of mechanism,it is found that the stronger the solvent polarity,the more electrons transfer from initiator to solvent through detailed energy decomposition analysis of electrostatic interactions between initiator and solvent molecules.Furthermore,we also found that the stronger the solvent polarity,the higher the monomer initiation energy barrier and the smaller the initiation rate coefficient.Counterintuitively,initiation is more favorable at lower temperatures based on the calculated results ofΔG_(TS).Finally,the kinetic characteristics in different solvents were further examined by kinetic modeling.It is found that in benzene and n-pentane,the polymerization rate exhibits first-order kinetics.While,slow initiation and fast propagation were observed in tetrahydrofuran(THF)due to the slow free ion formation rate,leading to a deviation from first-order kinetics.
文摘Renewable energy conversion as well as water electrolysis technologies are constrained by the fact that kinetics are always slow in the electrocatalytic oxygen evolution reaction(OER).There are numerous means and strategies for the enhancement of OER activity.In this paper,we systematically review the important role of anionic vacancies in enhancing the OER activity of catalysts:increasing catalyst conductivity,improving electrical conductivity,and enhancing intermediate adsorption.In order to better detect the presence of vacancies in the samples,the principle of vacancy detection is reviewed in detail in terms of both spectroscopic and microscopic characterization,and the methods of vacancy formation as well as the factors influencing the concentration of vacancies are summarized in detail.In addition,the challenges and new directions for the study of anionic vacancies are provided.Lei Wang was awarded a Ph.D.in chemistry from Jilin University in 2006 under the supervision of Prof.Shouhua Feng.He worked as a Postdoctoral Scholar in Shandong University,the State Key Laboratory of Crystal Materials from 2008 to 2010.He is currently a professor at Qingdao University of Science and Technology.His research interests mainly focus on the design and synthesis of functional organic-inorganic hybrids and porous MOFs materials,as well as their applications in photocatalysis,electrocatalysis,lithium-ion battery,etc.Jingqi Chi received her B.S.degree and Ph.D.degree from the State Key Laboratory of Heavy Oil Processing,China University of Petroleum(East China).She is currently an associate professor at Qing dao University of Science and Technology.Her research interests focus on the design and synthesis of transition metal-based nanostructures and porous MOFs materials for electrochemical applications.
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 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(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supports from the National Natural Science Foundation of China(No.22173089,No.21827804,and No.22103075)the National Key R&D Program of China(No.2021YFA0716801 and No.2017YFA0303502).
文摘A plasma injection ion source has been de-veloped for the photoelectron velocity imag-ing studies of metal-containing anions.The source employs a pulse discharge nozzle for generating a plasma beam that perpendicu-larly crosses the master supersonic jet beam from a home-made pulsed piezo valve.The discharge nozzle is designed for high voltage gas discharge with efficient metal sputtering of the cathode,and thus plays a role in met-al atom and ion source.Supersonically jet-cooled anions can be produced in the master gas jet via reactions of the plasma products.The source is integrated into a photoelectron ve-locity imaging spectrometer.Test mass spectrometry experiments show that the ion source can efficiently produce transition metal containing anions,such as FeO_(m)^(-),CuO_(m)^(-),CuC_(n)^(-),CuC_(n)O_(m)^(-).The photoelectron imaging results by photodetachment of O-show that the pho-toelectron energy resolution of the whole instrument isΔE/E≈2.3%,and the results of FeO^(-)indicate that internal temperatures of anions from the source could be efficiently cooled down.
