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
An effective strategy for enhancing the heat resistance of polystyrene(PS)with regard to its glass transition temperature(T_(g))involves the anionic solution copolymerization of a-methylstyrene(AMS)with styrene(St),ty...An effective strategy for enhancing the heat resistance of polystyrene(PS)with regard to its glass transition temperature(T_(g))involves the anionic solution copolymerization of a-methylstyrene(AMS)with styrene(St),typically requires much lower temperature(-25℃)and multistep monomer feeding to achieve higher number-average molecular weight(M_(n))block copolymers.However,the anionic copolymerization of AMS and St under the mild temperature remains largely unexplored.This study systematically investigated the anionic copolymerization of AMS and St using n-BuLi in nonpolar solvent(-25℃ to 25℃)through both one-step and two-step approaches.We demonstrated that one-step copolymerization at 25℃ yielded only 1-3 terminal AMS units,with higher feed ratios(5 wt%-20 wt%)increasing AMS incorporation but reducing the exact molecular weight(MW)due to enhanced depolymerization,as evidenced by MALDI-TOF MS.Temperature-controlled AMS conversion at-15℃ achieved 98%AMS conversion(5 wt% feed)by suppressing side reactions and lowering the[M]_(e),while 50℃(near T_(C))almost prevented incorporation.Despite t-BuOK regulation induced broader PDI(1.24)via reactive[(polymer-Li)OR]K intermediates,while other systems showed narrow distributions,t-BuOK outperformed THF in enhancing AMS incorporation via efficient ion pair dissociation.In comparison,the two-step polymerization approach demonstrated superior performance,achieving both higher AMS conversion efficiency and preferential incorporation at the initiation end.At a 20 wt%AMS feed ratio,this method yielded copolymer chains containing up to 6 AMS units on average.Thermal analysis revealed a composition-dependent single T_(g),which exhibited a systematic increase with higher AMS incorporation content.These results collectively demonstrate the precise control over AMS incorporation and heat resistance achievable through the manipulation of polymerization conditions.展开更多
Ion conduction in covalent-organic framework(COF)membranes is vital for energy conversion and storage.Conventional phenomenological methods based on the Arrhenius equation offer micrometer-scale cognition of ion condu...Ion conduction in covalent-organic framework(COF)membranes is vital for energy conversion and storage.Conventional phenomenological methods based on the Arrhenius equation offer micrometer-scale cognition of ion conduction,whereas they ignore atomic details of ion-pore interactions and sophisticated conduction mechanisms,leaving gaps in high-resolution and bottom-up understanding of ion conduction in a nanoconfined space.In this study,we develop a hierarchical approach by holistically synergizing electronic structure calculations,first-principles molecular dynamics simulations,and thermodynamic integration methods to investigate the conduction of chloride(Cl^(-))and hydroxide(OH^(-))ions in a COF membrane.It is revealed that Cl^(-)ion with symmetric charge distribution undergoes weak solvation and tight ion-pore binding,which results in a tortuous conduction pathway,a high energy barrier,and slow diffusion based on the vehicular mechanism.In remarkable contrast,OH^(-)ion with heterogeneous charge distribution features strong solvation and weak ion-pore binding,and it jumps frequently via a smooth pathway and a low energy barrier.Moreover,OH^(-)ion conduction follows a mixed vehicular and Grotthuss mechanism,causing highly mutable ion identity and number,as well as superior dynamics due to proton transfer.This hierarchical approach provides sub-nanometer resolution insights into ion conduction,guiding intelligent membrane design and performance regulation to control ion conduction for emerging applications.展开更多
Anion exchange membranes(AEMs)are pivotal for advancing fuel cells and water electrolysis.However,their widespread adoption is hindered by the sluggish ion transport and inadequate durability.Herein,by tuning the numb...Anion exchange membranes(AEMs)are pivotal for advancing fuel cells and water electrolysis.However,their widespread adoption is hindered by the sluggish ion transport and inadequate durability.Herein,by tuning the number of conjugated aromatic rings and the branching sites within the monomers,a series of hyperbranched poly(aryl piperidinium)AEMs with coplanar polycyclic aromatic units are prepared to address the poor mechanical properties of rigid conjugated AEMs.The results indicate that the introduction of planar-conjugated triphenylene(TY)units in the polymer backbone facilitates ordered interchain aggregation driven byπ-πstacking interaction to form well-defined ion-conductive channels while suppressing excessive swelling and enhancing the membrane stability.The hyperbranched AEM containing the TY units(QTPTY)possesses excellent mechanical properties with 55.9 MPa of stress and 60.3%of strain.Additionally,the QTPTY membrane achieves an exceptional OH-conductivity of 146.4 m S cm^(-1)at 80℃,with 94.7%conductivity retention and mechanical properties reduction below 2%after 1600 h in 2 M Na OH.In an H_(2)/O_(2) fuel cell,QTPTY delivers a peak power density of 1.43 W cm^(-2),surpassing linear and the other twoπ-conjugated hyperbranched analogs.In water electrolysis,the AEM exhibits a current density of 2.30 A cm^(-2)at 1.80 V,exceeding the 2026 targets of the U.S.Department of Energy.This work demonstrates that planar-conjugated hyperbranched architectures have a significant potential in designing robust,high-performance AEMs for sustainable energy technologies.展开更多
The practical application of lithium metal batteries(LMBs)requires electrolytes that simultaneously ensure high safety and interfacial stability.Although locally concentrated ionic liquid electrolytes(LCILEs)exhibit e...The practical application of lithium metal batteries(LMBs)requires electrolytes that simultaneously ensure high safety and interfacial stability.Although locally concentrated ionic liquid electrolytes(LCILEs)exhibit exceptional electrochemical stability and compatibility with electrode electrolyte interfaces(EEIs),two major challenges persist:(i)safety risks caused by excessive low-flash-point diluents,and(ii)insufficient understanding of how diluents modulate solvation structures.Herein,we introduce a low-diluent-content LCILE system composed of lithium bis(fluorosulfonyl)imide(LiFSI)salt,N-methyl-N-propyl-pyrrolidinium bis(fluorosulfonyl)imide(Pyr_(13)FSI)ionic liquid,and trifluoromethanesulfonate(TFS)diluent.The TFS diluent strengthens ion-ion interactions by lowering the dielectric constant of the electrolyte,resulting in the formation of a unique nanometric anion aggregates(N-AGGs)reinforced solvation structure.These large anionic clusters exhibit accelerated redox decomposition kinetics,facilitating the rapid formation of a thin,dense,and low-impedance EEI.Consequently,the Li/LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)coin cell achieves 87.8%capacity retention over 300 cycles at 4.3 V,while a practical 1.4 Ah Li/NCM622 pouch cell retains 84.5%capacity after 80 cycles at 4.5 V.Furthermore,the electrolyte demonstrates exceptional safety,and 2 Ah Li metal pouch cells successfully pass rigorous nail penetration tests without any ignition or explosion.This work not only provides a design strategy for intrinsically safe and high-performance electrolytes but also highlights the critical role of anion cluster decomposition kinetics in shaping EEI formation.展开更多
Developing practical anion exchange membrane water electrolysis(AEMWE)technology encounters great challenges in not only cell efficiency but also long-term durability due to mechanical electrocatalyst detachment and e...Developing practical anion exchange membrane water electrolysis(AEMWE)technology encounters great challenges in not only cell efficiency but also long-term durability due to mechanical electrocatalyst detachment and electrochemical dissolution of active species,especially for the anodic oxygen evolution reaction(OER).Herein,a"two-pronged"approach is proposed to construct organophosphorus-protected NiFe layered double hydroxide catalysts on plasma-modified substrate,serving as an efficient and robust anode for practical AEMWE.Mechanical tests combined with operando spectroscopies and theoretical calculations demonstrate that the plasma modification strengthens the catalyst-substrate adhesion,while the organophosphorus protection prevents Fe leaching and promotes reaction kinetics during OER.The resultant electrode delivers an ultralow overpotential of 276 mV at 1 A cm^(-2),together with a remarkable stability at 0.5 A cm^(-2)over 500 h.Furthermore,assembling the optimized anode into an AEMWE device contributes to a minimized cell voltage of 1.70 V at 1 A cm^(-2),which sustains durable green hydrogen production with an economical energy consumption of 4.16 kW h Nm^(-3)H_(2).展开更多
Elucidating the active site formation mechanism of bismuth(Bi)-based catalysts in electrochemical CO_(2)reduction remains challenging for achieving high activity,selectivity,and long-term stability.Here we confirm thr...Elucidating the active site formation mechanism of bismuth(Bi)-based catalysts in electrochemical CO_(2)reduction remains challenging for achieving high activity,selectivity,and long-term stability.Here we confirm through experimental results that Bi-based catalysts containing halogen ions(I^(-),Cl^(-),Br^(-))and SO_(4)^(2-)maintain the system stability,keeping Faraday efficiency of formic acid above90%in the current range of 50-800 mA cm^(-2).In contrast,anions containing S^(2-)and NO_(3)^(-)in the electrolyte can be reduced to produce by-products.These anions and their by-products could poison the active center,leading to increased side reactions and thus significantly reducing the Faraday efficiency of formic acid.The combination of non-in situ and in situ characterization results revealed that the Bi-based catalysts all underwent the transition from the initial state to the Bi/Bi_(2)O_(2)CO_(3)(BOC)intermediate state in high-concentration KHCO_(3) solution,and the different anions could selectively modulate the degree of exposure of specific crystalline surfaces of BOC.At the late stage of the reaction,BOC was completely converted to metal Bi and became the real active center.Combined with in situ IR and DFT calculations,it is further verified that^(*)OCHO is the key intermediate on the metallic Bi surface,which is most favorable for formic acid formation.This study reveals the key mechanism by which anions affect the formation of active sites via modulating the catalyst reconstruction process,which provides an important theoretical basis for the design and optimization of test conditions of Bi-based catalysts.展开更多
Aqueous zinc-ion batteries(AZIBs) have advantages including low economic cost and high safety.Nevertheless,the serious hydrogen evolution reactions(HER) and rampant growth of Zn dendrite hinder their further developme...Aqueous zinc-ion batteries(AZIBs) have advantages including low economic cost and high safety.Nevertheless,the serious hydrogen evolution reactions(HER) and rampant growth of Zn dendrite hinder their further development.Herein,potassium acetate(KAc) additive with cation/anion synergy effect is added into the ZnSO_(4) electrolyte to effectively promote the oriented uniform Zn deposition and suppress side reactions.According to density functional theory calculation and experimental results,CH_(3)COO^(-)(Ac^(-))anions are capable of forming stronger hydrogen bonds with H_(2)O molecules,leading to an expanded electrochemical stability window,reduced the reactivity of H_(2)O,and hence suppressing HER.Meanwhile,Ac-anions can also preferentially adsorb onto the Zn anode,promoting dense deposition towards the(100) crystal plane.Besides,dissociated K^(+) ions serve as electrostatic shielding cations,which significantly promote uniform Zn deposition and prevent dendrite formation.Thus,the Zn||Zn symmetric cell demonstrates an impressive cycle lifespan of 3000 h at 1.0 m A/cm^(2).Furthermore,the Zn||MnO_(2) full battery exhibits superior stability with a capacity retention of 86.95 % at 2.0 A/g after 4000 cycles.Therefore,the cation/anion synergy effect in KAc additive offers a viable solution to address HER and hinder dendrite growth at the interface of Zn anodes.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
BACKGROUND Chronic enteropathy associated with solute carrier organic anion transporter family member 2A1(SLCO2A1)(CEAS)is a rare autosomal recessive hereditary disease characterized by anemia,hypoproteinemia,abdomina...BACKGROUND Chronic enteropathy associated with solute carrier organic anion transporter family member 2A1(SLCO2A1)(CEAS)is a rare autosomal recessive hereditary disease characterized by anemia,hypoproteinemia,abdominal pain,diarrhea,and multiple shallow ulcers in the small intestine.Genetic analysis for SLCO2A1 mutations has identified more than 10 variant types,including the mostly reported c.940+1G>A splice site mutation.CASE SUMMARY Herein,we described a 33-year-old female patient who was admitted for anemia,edema,and a positive fecal occult blood test,unaccompanied by abdominal pain and diarrhea.She was diagnosed with CEAS due to compound heterozygous variants,c.940+1G>cA(splice-5)and c.1658T>A(p.Ile553Asn)in SLCO2A1,which had not been previously reported.Importantly,we reviewed 132 reported CEAS patients,which showed that anemia(87.3%)and hypoproteinemia(81%)were the most common symptoms.Nearly 25.8%of patients only had a positive result of fecal occult blood,without any symptoms of gastrointestinal bleeding.CONCLUSION In conclusion,fecal tests should be repeated in patients with anemia and edema to find clues for chronic enteropathy,including the rare cause-CEAS.展开更多
NASICON-type vanadium fluorophosphate is a promising cathode for sodium-ion batteries.Yet,the thermally-driven loss of undercoordinated dangling fluorine anions weakens its structural stability,which triggers severe f...NASICON-type vanadium fluorophosphate is a promising cathode for sodium-ion batteries.Yet,the thermally-driven loss of undercoordinated dangling fluorine anions weakens its structural stability,which triggers severe framework distortion from interconnected double-octahedral to isolated local octahedral units,as well as a degeneracy of t_(2g) electronic configuration of vanadium(V)3d orbit.In this work,it is clarified that such a degenerate state undergoes spontaneous lattice evolution to reduce the system energy,which causes a low crystalline symmetry and a parasitic V^(4+)/V^(3+)redox reaction in the low-voltage region.Herein,an anion-coordination regulation strategy is developed to suppress this degeneration by anchoring fluorine anions in the double-octahedral[V_(2)O_(8)F_(3)]framework.Density functional theory calculations and in-situ techniques track the F-anion-driven structural evolution and charge compensation mechanisms,revealing that this strategy mitigates detrimental phase segregation during the initial desodiation stage and enhances the Na^(+)diffusion kinetic rate over a factor of 100.Concurrently,this strategy releases the V^(4+)/V^(3+)redox kinetics by eliminating the parasitic low-voltage plateau.The full-cell assembled with the optimized fluorophosphate cathode delivers an increase of 50%in discharge capacity and stable two-voltage-plateau behavior,enabled by its double-octahedral[V_(2)O_(8)F_(3)]polyanionic structure that facilitates unimpeded three-dimensional(3D)Na^(+)transport.By correlating anion-coordination stability with orbital-level charge compensation,this work establishes a universal paradigm for highperformance polyanionic cathodes,positioning it as a competitive candidate for battery applications.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
Obstructive jaundice occurs in patients suffering from cholelithiasis and from neoplasms affecting the pancreas and the common bile duct.The absorption,distribution and elimination of drugs are impaired during this pa...Obstructive jaundice occurs in patients suffering from cholelithiasis and from neoplasms affecting the pancreas and the common bile duct.The absorption,distribution and elimination of drugs are impaired during this pathology.Prolonged cholestasis may alter both liver and kidney function.Lactam antibiotics,diuretics,non-steroidal anti-inflammatory drugs,several antiviral drugs as well as endogenous compounds are classified as organic anions.The hepatic and renal organic anion transport pathways play a key role in the pharmacokinetics of these compounds.It has been demonstrated that acute extrahepatic cholestasis is associated with increased renal elimination of organic anions.The present work describes the molecular mechanisms involved in the regulation of the expression and function of the renal and hepatic organic anion transporters in extrahepatic cholestasis,such as multidrug resistanceassociated protein 2,organic anion transporting polypeptide 1,organic anion transporter 3,bilitranslocase,bromosulfophthalein/bilirubin binding protein,organic anion transporter 1 and sodium dependent bile salt transporter.The modulation in the expression of renal organic anion transporters constitutes a compensatory mechanism to overcome the hepatic dysfunction in the elimination of organic anions.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
Anion exchange membrane(AEM),as a kind of key membrane materials,has shown great application potential in many electrochemical fields,and remarkable progress has been made in related research in recent years.In this p...Anion exchange membrane(AEM),as a kind of key membrane materials,has shown great application potential in many electrochemical fields,and remarkable progress has been made in related research in recent years.In this paper,the research status of AEM is reviewed,including its material design,preparation method,performance optimization and application in the fields of hydrogen production by electrolytic water,fuel cell and water treatment.In terms of material design,new polymer skeleton structures are emerging to regulate the stability of ion conduction channels and membranes by introducing specific functional groups or changing the molecular chain structure.The preparation methods have been gradually expanded from the traditional solution casting method to more advanced technologies,such as interfacial polymerization and electrostatic spinning,which effectively improve the microstructure and property uniformity of the film.Performance optimization focuses on improving ion conductivity,reducing membrane swelling rate and enhancing chemical stability,and a variety of modification strategies are developed and applied.Despite the achievements made so far,there are still some challenges,such as the lack of long-term stability in highly alkaline environments.Future research needs to further explore new material systems and preparation processes in order to promote the wide application and sustainable development of AEM technology in energy,environmental protection and other fields.展开更多
Ni_(2)CoS_(4)was prepared by the liquid‑phase method and applied to the benzyl alcohol electro‑oxidation reaction(BAOR),demonstrating excellent catalytic activity[with a current density of 271 mA·cm^(-2)at 1.40 V...Ni_(2)CoS_(4)was prepared by the liquid‑phase method and applied to the benzyl alcohol electro‑oxidation reaction(BAOR),demonstrating excellent catalytic activity[with a current density of 271 mA·cm^(-2)at 1.40 V(vs RHE)]and long‑term stability.The S‑anion effect can regulate the charge distribution on the catalyst surface,thereby enhancing the additional adsorption capacity of OH-at the Co sites.By combining material characterization and theoretical calculations,it can be observed that this process can increase the concentration of the OH^(*)intermediate,accelerate the activation process of the Ni site,and ultimately achieve an improvement in overall activity and stability.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
In order to find the optimal anions and cations for designing energetic salts with excellent detonation properties,the properties of 140 salts formed from the anions(A–G)of 3,3′-dinitroamino-4,4′-azoxyfurazan(DAAF)...In order to find the optimal anions and cations for designing energetic salts with excellent detonation properties,the properties of 140 salts formed from the anions(A–G)of 3,3′-dinitroamino-4,4′-azoxyfurazan(DAAF)derivatives substituted with the—NH_(2),—N_(3) or—NO_(2) group and the cations(1–20)of guanidine,triazole,or tetrazole derivatives were investigated by means of density-functional theory.The predicted densities,heats of formation,detonation velocities(D),and detonation pressures(P)of 140 salts were 11.72 to 2.06 g·cm ^(−3),570.2 to 2333.4 kJ·mol^(−1),8.29 to 10.02 km·s^(−1) and 30.16 to 47.57 GPa,respectively.Most of the salts had better detonation properties than the widely used hexahydro-1,3,5-trinitro-1,3,5-triazine(RDX).Salts containing—NO_(2) group anions(C and F)have better detonation properties(D is 8.88 to 10.02 km·s^(−1) and P is 35.75 to 47.75 GPa)than other salts.Salts containing the cations NH_(4)^(+)(1),NH_(3)OH^(+)(2)and CH_(2)N_(4)NO_(2)^(+)(20)had good detonation properties(D is 9.38 to 10.02 km·s^(−1) and P is 40.72 to 47.75 GPa).Depending on the detonation properties,anions(C and F)and cations(1,2 and 20)are the recommended ions for the generation of energetic salts.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
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financially supported by the National Natural Science Foundation of China(No.52373052)Fundamental Research Funds for the Central Universities(No.DUT24MS011)。
文摘An effective strategy for enhancing the heat resistance of polystyrene(PS)with regard to its glass transition temperature(T_(g))involves the anionic solution copolymerization of a-methylstyrene(AMS)with styrene(St),typically requires much lower temperature(-25℃)and multistep monomer feeding to achieve higher number-average molecular weight(M_(n))block copolymers.However,the anionic copolymerization of AMS and St under the mild temperature remains largely unexplored.This study systematically investigated the anionic copolymerization of AMS and St using n-BuLi in nonpolar solvent(-25℃ to 25℃)through both one-step and two-step approaches.We demonstrated that one-step copolymerization at 25℃ yielded only 1-3 terminal AMS units,with higher feed ratios(5 wt%-20 wt%)increasing AMS incorporation but reducing the exact molecular weight(MW)due to enhanced depolymerization,as evidenced by MALDI-TOF MS.Temperature-controlled AMS conversion at-15℃ achieved 98%AMS conversion(5 wt% feed)by suppressing side reactions and lowering the[M]_(e),while 50℃(near T_(C))almost prevented incorporation.Despite t-BuOK regulation induced broader PDI(1.24)via reactive[(polymer-Li)OR]K intermediates,while other systems showed narrow distributions,t-BuOK outperformed THF in enhancing AMS incorporation via efficient ion pair dissociation.In comparison,the two-step polymerization approach demonstrated superior performance,achieving both higher AMS conversion efficiency and preferential incorporation at the initiation end.At a 20 wt%AMS feed ratio,this method yielded copolymer chains containing up to 6 AMS units on average.Thermal analysis revealed a composition-dependent single T_(g),which exhibited a systematic increase with higher AMS incorporation content.These results collectively demonstrate the precise control over AMS incorporation and heat resistance achievable through the manipulation of polymerization conditions.
基金supported by the National Science Foundation for Distinguished Young Scholars,China(No.52025065)the Key Research and Development Program of Shaanxi,China(No.2023GXLH-016)+3 种基金A*STAR LCER-FI,Singapore projects(LCERFI010015 U2102d2004 and LCERFI01-0033 U2102d2006)the National Research Foundation Singapore(NRF-CRP26-2021RS0002)the China Scholarship Council Program,China(Project ID:202306280178)for financial supportthe support of the Computing Center in Xi’an。
文摘Ion conduction in covalent-organic framework(COF)membranes is vital for energy conversion and storage.Conventional phenomenological methods based on the Arrhenius equation offer micrometer-scale cognition of ion conduction,whereas they ignore atomic details of ion-pore interactions and sophisticated conduction mechanisms,leaving gaps in high-resolution and bottom-up understanding of ion conduction in a nanoconfined space.In this study,we develop a hierarchical approach by holistically synergizing electronic structure calculations,first-principles molecular dynamics simulations,and thermodynamic integration methods to investigate the conduction of chloride(Cl^(-))and hydroxide(OH^(-))ions in a COF membrane.It is revealed that Cl^(-)ion with symmetric charge distribution undergoes weak solvation and tight ion-pore binding,which results in a tortuous conduction pathway,a high energy barrier,and slow diffusion based on the vehicular mechanism.In remarkable contrast,OH^(-)ion with heterogeneous charge distribution features strong solvation and weak ion-pore binding,and it jumps frequently via a smooth pathway and a low energy barrier.Moreover,OH^(-)ion conduction follows a mixed vehicular and Grotthuss mechanism,causing highly mutable ion identity and number,as well as superior dynamics due to proton transfer.This hierarchical approach provides sub-nanometer resolution insights into ion conduction,guiding intelligent membrane design and performance regulation to control ion conduction for emerging applications.
基金the financial support from the National Natural Science Foundation of China(Grant Nos.22278340&22078272)。
文摘Anion exchange membranes(AEMs)are pivotal for advancing fuel cells and water electrolysis.However,their widespread adoption is hindered by the sluggish ion transport and inadequate durability.Herein,by tuning the number of conjugated aromatic rings and the branching sites within the monomers,a series of hyperbranched poly(aryl piperidinium)AEMs with coplanar polycyclic aromatic units are prepared to address the poor mechanical properties of rigid conjugated AEMs.The results indicate that the introduction of planar-conjugated triphenylene(TY)units in the polymer backbone facilitates ordered interchain aggregation driven byπ-πstacking interaction to form well-defined ion-conductive channels while suppressing excessive swelling and enhancing the membrane stability.The hyperbranched AEM containing the TY units(QTPTY)possesses excellent mechanical properties with 55.9 MPa of stress and 60.3%of strain.Additionally,the QTPTY membrane achieves an exceptional OH-conductivity of 146.4 m S cm^(-1)at 80℃,with 94.7%conductivity retention and mechanical properties reduction below 2%after 1600 h in 2 M Na OH.In an H_(2)/O_(2) fuel cell,QTPTY delivers a peak power density of 1.43 W cm^(-2),surpassing linear and the other twoπ-conjugated hyperbranched analogs.In water electrolysis,the AEM exhibits a current density of 2.30 A cm^(-2)at 1.80 V,exceeding the 2026 targets of the U.S.Department of Energy.This work demonstrates that planar-conjugated hyperbranched architectures have a significant potential in designing robust,high-performance AEMs for sustainable energy technologies.
基金supported by the National Key R&D Program of China(Grant No.2022YFE0207300)the National Natural Science Foundation of China(Grant Nos.22179142 and 22075314)+1 种基金Jiangsu Provincial Science and Technology Program(Grant No.BG 2024020).XPSWAXS and TOF-SIMS characterizations were supported by Nano-X(Vacuum Interconnected Nanotech Workstation,Suzhou Institute of Nano-Tech and Nano-Bionics,Chinese Academy of Sciences(SINANO),Suzhou 215123,China)。
文摘The practical application of lithium metal batteries(LMBs)requires electrolytes that simultaneously ensure high safety and interfacial stability.Although locally concentrated ionic liquid electrolytes(LCILEs)exhibit exceptional electrochemical stability and compatibility with electrode electrolyte interfaces(EEIs),two major challenges persist:(i)safety risks caused by excessive low-flash-point diluents,and(ii)insufficient understanding of how diluents modulate solvation structures.Herein,we introduce a low-diluent-content LCILE system composed of lithium bis(fluorosulfonyl)imide(LiFSI)salt,N-methyl-N-propyl-pyrrolidinium bis(fluorosulfonyl)imide(Pyr_(13)FSI)ionic liquid,and trifluoromethanesulfonate(TFS)diluent.The TFS diluent strengthens ion-ion interactions by lowering the dielectric constant of the electrolyte,resulting in the formation of a unique nanometric anion aggregates(N-AGGs)reinforced solvation structure.These large anionic clusters exhibit accelerated redox decomposition kinetics,facilitating the rapid formation of a thin,dense,and low-impedance EEI.Consequently,the Li/LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)coin cell achieves 87.8%capacity retention over 300 cycles at 4.3 V,while a practical 1.4 Ah Li/NCM622 pouch cell retains 84.5%capacity after 80 cycles at 4.5 V.Furthermore,the electrolyte demonstrates exceptional safety,and 2 Ah Li metal pouch cells successfully pass rigorous nail penetration tests without any ignition or explosion.This work not only provides a design strategy for intrinsically safe and high-performance electrolytes but also highlights the critical role of anion cluster decomposition kinetics in shaping EEI formation.
基金supported by the Natural Science Foundation of Shanghai Municipality(25ZR1401027)the National Natural Science Foundation of China(22572041,11975081,22309037,52274297,and 22402083)+1 种基金Hainan Provincial Natural Science Foundation of China(225YXQN587)Start-up Research Foundation of Hainan University(KYQD(ZR)23035)。
文摘Developing practical anion exchange membrane water electrolysis(AEMWE)technology encounters great challenges in not only cell efficiency but also long-term durability due to mechanical electrocatalyst detachment and electrochemical dissolution of active species,especially for the anodic oxygen evolution reaction(OER).Herein,a"two-pronged"approach is proposed to construct organophosphorus-protected NiFe layered double hydroxide catalysts on plasma-modified substrate,serving as an efficient and robust anode for practical AEMWE.Mechanical tests combined with operando spectroscopies and theoretical calculations demonstrate that the plasma modification strengthens the catalyst-substrate adhesion,while the organophosphorus protection prevents Fe leaching and promotes reaction kinetics during OER.The resultant electrode delivers an ultralow overpotential of 276 mV at 1 A cm^(-2),together with a remarkable stability at 0.5 A cm^(-2)over 500 h.Furthermore,assembling the optimized anode into an AEMWE device contributes to a minimized cell voltage of 1.70 V at 1 A cm^(-2),which sustains durable green hydrogen production with an economical energy consumption of 4.16 kW h Nm^(-3)H_(2).
基金funded by the“Pioneer”and“Leading Goose”R&D Program of Zhejiang(No.2023C03017)China Postdoctoral Science Foundation(No.GZC20230373)+5 种基金Zhejiang Provincial Natural Science Foundation of China(No.LQ24B070010)CMA Key Open Laboratory of Transforming Climate Resources to Economy(No.2024004K)Natural Science Foundation of Huzhou City(No.2024YZ19)the National Natural Science Foundation of China(Nos.22202032,22406020 and 22406019)the Key Research and Development Projects of Xinjiang Uygur Autonomous Region,China(No.2022B02031)Joint Fund of the Zhejiang Provincial Natural Science Foundation of China(No.LBMHY25E060009)。
文摘Elucidating the active site formation mechanism of bismuth(Bi)-based catalysts in electrochemical CO_(2)reduction remains challenging for achieving high activity,selectivity,and long-term stability.Here we confirm through experimental results that Bi-based catalysts containing halogen ions(I^(-),Cl^(-),Br^(-))and SO_(4)^(2-)maintain the system stability,keeping Faraday efficiency of formic acid above90%in the current range of 50-800 mA cm^(-2).In contrast,anions containing S^(2-)and NO_(3)^(-)in the electrolyte can be reduced to produce by-products.These anions and their by-products could poison the active center,leading to increased side reactions and thus significantly reducing the Faraday efficiency of formic acid.The combination of non-in situ and in situ characterization results revealed that the Bi-based catalysts all underwent the transition from the initial state to the Bi/Bi_(2)O_(2)CO_(3)(BOC)intermediate state in high-concentration KHCO_(3) solution,and the different anions could selectively modulate the degree of exposure of specific crystalline surfaces of BOC.At the late stage of the reaction,BOC was completely converted to metal Bi and became the real active center.Combined with in situ IR and DFT calculations,it is further verified that^(*)OCHO is the key intermediate on the metallic Bi surface,which is most favorable for formic acid formation.This study reveals the key mechanism by which anions affect the formation of active sites via modulating the catalyst reconstruction process,which provides an important theoretical basis for the design and optimization of test conditions of Bi-based catalysts.
基金financially supported by the National Natural Science Foundation of China (No.52372188)the 111 Project (No.D17007)2023 Introduction of studying abroad talent program。
文摘Aqueous zinc-ion batteries(AZIBs) have advantages including low economic cost and high safety.Nevertheless,the serious hydrogen evolution reactions(HER) and rampant growth of Zn dendrite hinder their further development.Herein,potassium acetate(KAc) additive with cation/anion synergy effect is added into the ZnSO_(4) electrolyte to effectively promote the oriented uniform Zn deposition and suppress side reactions.According to density functional theory calculation and experimental results,CH_(3)COO^(-)(Ac^(-))anions are capable of forming stronger hydrogen bonds with H_(2)O molecules,leading to an expanded electrochemical stability window,reduced the reactivity of H_(2)O,and hence suppressing HER.Meanwhile,Ac-anions can also preferentially adsorb onto the Zn anode,promoting dense deposition towards the(100) crystal plane.Besides,dissociated K^(+) ions serve as electrostatic shielding cations,which significantly promote uniform Zn deposition and prevent dendrite formation.Thus,the Zn||Zn symmetric cell demonstrates an impressive cycle lifespan of 3000 h at 1.0 m A/cm^(2).Furthermore,the Zn||MnO_(2) full battery exhibits superior stability with a capacity retention of 86.95 % at 2.0 A/g after 4000 cycles.Therefore,the cation/anion synergy effect in KAc additive offers a viable solution to address HER and hinder dendrite growth at the interface of Zn anodes.
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(General Program),No.82000493Peking University People’s Hospital Scientific Research Development Funds,No.RDJP2023-09.
文摘BACKGROUND Chronic enteropathy associated with solute carrier organic anion transporter family member 2A1(SLCO2A1)(CEAS)is a rare autosomal recessive hereditary disease characterized by anemia,hypoproteinemia,abdominal pain,diarrhea,and multiple shallow ulcers in the small intestine.Genetic analysis for SLCO2A1 mutations has identified more than 10 variant types,including the mostly reported c.940+1G>A splice site mutation.CASE SUMMARY Herein,we described a 33-year-old female patient who was admitted for anemia,edema,and a positive fecal occult blood test,unaccompanied by abdominal pain and diarrhea.She was diagnosed with CEAS due to compound heterozygous variants,c.940+1G>cA(splice-5)and c.1658T>A(p.Ile553Asn)in SLCO2A1,which had not been previously reported.Importantly,we reviewed 132 reported CEAS patients,which showed that anemia(87.3%)and hypoproteinemia(81%)were the most common symptoms.Nearly 25.8%of patients only had a positive result of fecal occult blood,without any symptoms of gastrointestinal bleeding.CONCLUSION In conclusion,fecal tests should be repeated in patients with anemia and edema to find clues for chronic enteropathy,including the rare cause-CEAS.
基金supported by the National Key Research and Development Program of China(2023YFB2406100)the National Natural Science Foundation of China(Grant No.22075062 and U23A20573)+6 种基金the Heilongjiang Touyan Team(Grant No.HITTY20190033)the Heilongjiang Postdoctoral Financial Assistance(Grant No.LBH-Z23137)the Postdoctoral Fellowship Program of CPSF(Grant No.GZC20233448)the China Postdoctoral Science Foundation(Grant No.2024M754198)the Shenzhen Science and Technology Program(KCXST20221021111216037)the Fundamental Research Funds for the Central Universities(Grant No.FRFCU5710051922)the program of “Open bidding for selecting the best candidates”(Grant No.2023JCA06)from Jiangxi Fuzhou Municipal Government。
文摘NASICON-type vanadium fluorophosphate is a promising cathode for sodium-ion batteries.Yet,the thermally-driven loss of undercoordinated dangling fluorine anions weakens its structural stability,which triggers severe framework distortion from interconnected double-octahedral to isolated local octahedral units,as well as a degeneracy of t_(2g) electronic configuration of vanadium(V)3d orbit.In this work,it is clarified that such a degenerate state undergoes spontaneous lattice evolution to reduce the system energy,which causes a low crystalline symmetry and a parasitic V^(4+)/V^(3+)redox reaction in the low-voltage region.Herein,an anion-coordination regulation strategy is developed to suppress this degeneration by anchoring fluorine anions in the double-octahedral[V_(2)O_(8)F_(3)]framework.Density functional theory calculations and in-situ techniques track the F-anion-driven structural evolution and charge compensation mechanisms,revealing that this strategy mitigates detrimental phase segregation during the initial desodiation stage and enhances the Na^(+)diffusion kinetic rate over a factor of 100.Concurrently,this strategy releases the V^(4+)/V^(3+)redox kinetics by eliminating the parasitic low-voltage plateau.The full-cell assembled with the optimized fluorophosphate cathode delivers an increase of 50%in discharge capacity and stable two-voltage-plateau behavior,enabled by its double-octahedral[V_(2)O_(8)F_(3)]polyanionic structure that facilitates unimpeded three-dimensional(3D)Na^(+)transport.By correlating anion-coordination stability with orbital-level charge compensation,this work establishes a universal paradigm for highperformance polyanionic cathodes,positioning it as a competitive candidate for battery applications.
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.
基金Supported by Grants from FONCYT(PICT 2007,No.00966, PICT 2010,No.2127)CONICET(PIP 2009-2011,No.1665, PIP2012-2015,No.00014)UNR PID(2008-2011/2012-2015)
文摘Obstructive jaundice occurs in patients suffering from cholelithiasis and from neoplasms affecting the pancreas and the common bile duct.The absorption,distribution and elimination of drugs are impaired during this pathology.Prolonged cholestasis may alter both liver and kidney function.Lactam antibiotics,diuretics,non-steroidal anti-inflammatory drugs,several antiviral drugs as well as endogenous compounds are classified as organic anions.The hepatic and renal organic anion transport pathways play a key role in the pharmacokinetics of these compounds.It has been demonstrated that acute extrahepatic cholestasis is associated with increased renal elimination of organic anions.The present work describes the molecular mechanisms involved in the regulation of the expression and function of the renal and hepatic organic anion transporters in extrahepatic cholestasis,such as multidrug resistanceassociated protein 2,organic anion transporting polypeptide 1,organic anion transporter 3,bilitranslocase,bromosulfophthalein/bilirubin binding protein,organic anion transporter 1 and sodium dependent bile salt transporter.The modulation in the expression of renal organic anion transporters constitutes a compensatory mechanism to overcome the hepatic dysfunction in the elimination of organic anions.
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“Grassland Talents”of Inner Mongolia Autonomous Region,Young Talents of Science and Technology in Universities of Inner Mongolia Autonomous Region(NJYT23030)Technology Breakthrough Engineering Hydrogen Energy Field“Unveiling and Leading”Project(2024KJTW0018)+3 种基金“Steed Plan High Level Talents”of Inner Mongolia University,Carbon neutralization research project(STZX202218)National Natural Science Foundation of China(U22A20107),Inner Mongolia Autonomous Region Natural Science Foundation(2023MS02002)Guangdong Provincial Key Laboratory of Materials and Technologies for Energy Conversion(MATEC2024KF011)National Key R&D Program of China(2022YFA1205201).
文摘Anion exchange membrane(AEM),as a kind of key membrane materials,has shown great application potential in many electrochemical fields,and remarkable progress has been made in related research in recent years.In this paper,the research status of AEM is reviewed,including its material design,preparation method,performance optimization and application in the fields of hydrogen production by electrolytic water,fuel cell and water treatment.In terms of material design,new polymer skeleton structures are emerging to regulate the stability of ion conduction channels and membranes by introducing specific functional groups or changing the molecular chain structure.The preparation methods have been gradually expanded from the traditional solution casting method to more advanced technologies,such as interfacial polymerization and electrostatic spinning,which effectively improve the microstructure and property uniformity of the film.Performance optimization focuses on improving ion conductivity,reducing membrane swelling rate and enhancing chemical stability,and a variety of modification strategies are developed and applied.Despite the achievements made so far,there are still some challenges,such as the lack of long-term stability in highly alkaline environments.Future research needs to further explore new material systems and preparation processes in order to promote the wide application and sustainable development of AEM technology in energy,environmental protection and other fields.
文摘Ni_(2)CoS_(4)was prepared by the liquid‑phase method and applied to the benzyl alcohol electro‑oxidation reaction(BAOR),demonstrating excellent catalytic activity[with a current density of 271 mA·cm^(-2)at 1.40 V(vs RHE)]and long‑term stability.The S‑anion effect can regulate the charge distribution on the catalyst surface,thereby enhancing the additional adsorption capacity of OH-at the Co sites.By combining material characterization and theoretical calculations,it can be observed that this process can increase the concentration of the OH^(*)intermediate,accelerate the activation process of the Ni site,and ultimately achieve an improvement in overall activity and stability.
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.
文摘In order to find the optimal anions and cations for designing energetic salts with excellent detonation properties,the properties of 140 salts formed from the anions(A–G)of 3,3′-dinitroamino-4,4′-azoxyfurazan(DAAF)derivatives substituted with the—NH_(2),—N_(3) or—NO_(2) group and the cations(1–20)of guanidine,triazole,or tetrazole derivatives were investigated by means of density-functional theory.The predicted densities,heats of formation,detonation velocities(D),and detonation pressures(P)of 140 salts were 11.72 to 2.06 g·cm ^(−3),570.2 to 2333.4 kJ·mol^(−1),8.29 to 10.02 km·s^(−1) and 30.16 to 47.57 GPa,respectively.Most of the salts had better detonation properties than the widely used hexahydro-1,3,5-trinitro-1,3,5-triazine(RDX).Salts containing—NO_(2) group anions(C and F)have better detonation properties(D is 8.88 to 10.02 km·s^(−1) and P is 35.75 to 47.75 GPa)than other salts.Salts containing the cations NH_(4)^(+)(1),NH_(3)OH^(+)(2)and CH_(2)N_(4)NO_(2)^(+)(20)had good detonation properties(D is 9.38 to 10.02 km·s^(−1) and P is 40.72 to 47.75 GPa).Depending on the detonation properties,anions(C and F)and cations(1,2 and 20)are the recommended ions for the generation of energetic salts.
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.
