Prussian blue/Prussian blue analogues(PB/PBAs)are widely used in electrochemistry and materials science fields,such as electrochemical energy storage,catalysis,water purification,and electromagnetic wave absorption,ow...Prussian blue/Prussian blue analogues(PB/PBAs)are widely used in electrochemistry and materials science fields,such as electrochemical energy storage,catalysis,water purification,and electromagnetic wave absorption,owing to their 3D open-framework structure,tunable composition,and large specific surface area.However,the co-precipitation method,which is most suitable for large-scale production of PB/PBAs,often leads to the formation of numerous crystal defects and severe lattice distortion,which significantly affects the structural stability of PB/PBAs.To obtain high-crystallinity PB/PBAs with targeted properties,precise synthesis considering various detailed conditions is especially needed.Herein,this review comprehensively summarizes the fundamental structure composition,key factors in synthesis,and applications in the electrochemistry of PB/PBAs.Unlike previous reports,this review elucidates the relationship between the physicochemical properties of PB/PBAs and their structural composition,with a particular focus on revealing the mechanisms and significance of specific preparation methods during the synthesis process,including reactant concentration,chelating agent,aging,atmosphere,temperature,and drying conditions,for achieving the precise fabrication of PB/PBAs nanomaterials.As PB/PBAs gradually become materials for multidimensional applications,we urge greater attention to the unique properties of PB/PBAs that are sustained by high crystallinity and stable crystal structures.This will effectively ensure the maximization of their advantages in practical applications.展开更多
Lithium-ion batteries(LIBs)have dominated the portable electronic and electrochemical energy markets since their commercialisation,whose high cost and lithium scarcity have prompted the development of other alkali-ion...Lithium-ion batteries(LIBs)have dominated the portable electronic and electrochemical energy markets since their commercialisation,whose high cost and lithium scarcity have prompted the development of other alkali-ion batteries(AIBs)including sodium-ion batteries(SIBs)and potassium-ion batteries(PIBs).Owing to larger ion sizes of Na^(+)and K^(+)compared with Li^(+),nanocomposites with excellent crystallinity orientation and well-developed porosity show unprecedented potential for advanced lithium/sodium/potassium storage.With enticing open rigid framework structures,Prussian blue analogues(PBAs)remain promising self-sacrificial templates for the preparation of various nanocomposites,whose appeal originates from the well-retained porous structures and exceptional electrochemical activities after thermal decomposition.This review focuses on the recent progress of PBA-derived nanocomposites from their fabrication,lithium/sodium/potassium storage mechanism,and applications in AIBs(LIBs,SIBs,and PIBs).To distinguish various PBA derivatives,the working mechanism and applications of PBA-templated metal oxides,metal chalcogenides,metal phosphides,and other nanocomposites are systematically evaluated,facilitating the establishment of a structure–activity correlation for these materials.Based on the fruitful achievements of PBA-derived nanocomposites,perspectives for their future development are envisioned,aiming to narrow down the gap between laboratory study and industrial reality.展开更多
ⅢThe superior adaptability of Prussian blue analogues(PBAs)in interacting with potassium ions has shifted research focus toward their potential application as cathodes of potassium-ion batteries(PIBs).The large inter...ⅢThe superior adaptability of Prussian blue analogues(PBAs)in interacting with potassium ions has shifted research focus toward their potential application as cathodes of potassium-ion batteries(PIBs).The large interstitial space formed between metal ions and–C≡N–in PBAs can accommodate large-radius K^(+).However,the rapid nucleation in the co-precipitation synthesis process of PBAs induces many lattice defects of[M(CN)_(6)]^(4-)vacancies(V_([M–C≡N])),interstitial and coordinated H_(2)O molecules,which will directly lead to performance degradation.Moreover,originating from various transition metal elements in low/high-spin electron configuration states,PBAs exhibit diverse electrochemical behaviors,such as low reaction kinetics of low-spin iron(Ⅱ),Jahn-Teller distortion and dissolution of manganese(Ⅲ),and electrochemical inertness of nickel(Ⅱ)and copper(Ⅱ).Here,we summarize recently reported structures and properties of PBAs,classifying them based on the types of transition metals(iron,cobalt,manganese,copper,nickel)employed.Advanced synthesis strategies,including control engineering of crystallinity based on H_(2)O molecules and V_([M–C≡N]),were discussed.Also,the approaches for enhancing the electrochemical performance of PBAs were highlighted.Finally,the challenges and prospects towards the future development of PBAs are put forward.The review is expected to provide technical and theoretical support for the design of high-performance PBAs.展开更多
Iron-based Prussian white(PW)materials have attracted considerable attention as promising cathodes for potassium-ion batteries(PIBs)due to their high capacity,easy preparation,and economic merits.However,the intrinsic...Iron-based Prussian white(PW)materials have attracted considerable attention as promising cathodes for potassium-ion batteries(PIBs)due to their high capacity,easy preparation,and economic merits.However,the intrinsic iron dissolution and uncontrollable cathode-electrolyte interface(CEI)formation in conventional organic electrolytes severely hinder their long-term cycling stability.Herein,we employ succinonitrile(SN),a bifunctional electrolyte additive,to suppress the iron dissolution and promote thin,uniform,and stable CEI formation of the PW cathode,thus improving its structural stability.Benefited from the coordination between the cyano groups in SN and iron atoms,this molecule can preferentially adsorb on the surface of PW to mitigate iron dissolution.SN also facilitates the decomposition of anions in potassium salt rather than organic solvents in electrolyte due to the attractive reaction between SN and anions.Consequently,the PW cathode with SN additive provides better electrochemical reversibility,showing capacity retention of 93.6%after 3000 cycles at 5C.In comparison,without SN,the capacity retention is only 87.4%after 1000 cycles under the same conditions.Moreover,the full cells of PW matched with commercial graphite(Gr)achieve stable cycling for 3500 cycles at a high rate of 20C,with an exceptional capacity decay of only 0.005%per cycle,surpassing the majority of recently reported results in literature.展开更多
The removal of cesium-137(^(137)Cs)from nuclear wastewater remains crucial due to its radioactivity and high solubility in water,which pose serious risk to human health and the environment.Aiming at selective capture ...The removal of cesium-137(^(137)Cs)from nuclear wastewater remains crucial due to its radioactivity and high solubility in water,which pose serious risk to human health and the environment.Aiming at selective capture of Cs^(+) from wastewater,a core-shell adsorbent,Prussian blue analog@y-alumina(PBA@Al_(2)O_(3))pellets were synthesized using the hydrothermal-stepwise deposition method.The coreshell PBA@Al_(2)O_(3)pellets showcased a PBA loading of 25%and demonstrated a maximum adsorption capacity of 15.65 mg·g^(-1).The adsorption data was consistent with the pseudo-second-order kinetic model and the Langmuir isotherm model.It effectively reduced bulk Cs^(+) concentrations from an initial 6.62 mg·L^(-1)to 2 μg·L^(-1),achieving a removal efficiency of 99.97%and distribution coefficient(Kd)of 1.265×10^(6)ml·g^(-1),surpassing the performance of other PBA-based materials.The material also indicated good mechanical properties and cesium ion removal rates of 99.7%across a wide pH range(1.82 to 11.12).Furthermore,PBA@Al_(2)O_(3)exhibited consistent removal rate of over 99%and good selectivity(SF=50-1600)towards Cs^(+) even in the presence of interfering ions such as Na^(+),K^(+),Mg^(2+),and Ca^(2+)ions.The Kd(Cs^(+))for PBA@Al2O3 in simulated seawater and groundwater were 9.92×10^(3)and 2.23×10^(4)ml·g^(-1),where the removal rates reached 96.1%and 98.2%,respectively.XPS confirms that the adsorption mechanism is the ion exchange between Cs^(+) and K^(+)ions.This study underscores the significant potential of inorganic core-shell pellets adsorbents as promising agents for the selective capture of Cs^(+) from wastewater.展开更多
Bimetallic oxides are promising electrocatalysts due to their rich composition,facile synthesis,and favorable stability under oxidizing conditions.This paper innovatively proposes a strategy aimed at constructing a on...Bimetallic oxides are promising electrocatalysts due to their rich composition,facile synthesis,and favorable stability under oxidizing conditions.This paper innovatively proposes a strategy aimed at constructing a one-dimensional heterostructure(Fe–NiO/NiMoO_(4) nanoparticles/nanofibers).The strategy commences with the meticulous treatment of NiMoO_(4) nanofibers,utilizing in situ etching techniques to induce the formation of Prussian Blue Analog compounds.In this process,[Fe(CN)_(6)]^(3-)anions react with the NiMoO_(4) host layer to form a steady NiFe PBA.Subsequently,the surface/interface reconstituted NiMoO_(4) nanofibers undergo direct oxidation,leading to a reconfiguration of the surface structure and the formation of a unique Fe–NiO/NiMoO_(4) one-dimensional heterostructure.The catalyst showed markedly enhanced electrocatalytic performance for the oxygen evolution reaction.Density functional theory results reveal that the incorporation of Fe as a dopant dramatically reduces the Gibbs free energy associated with the rate-determining step in the oxygen evolution reaction pathway.This pivotal transformation directly lowers the activation energy barrier,thereby significantly enhancing electron transfer efficiency.展开更多
The traditional nanozymes-based ratiometric fluorescence sensing platforms usually necessitate the supplementary addition of fluorescent probes,therefore greatly restricting its convenient and broad application.In thi...The traditional nanozymes-based ratiometric fluorescence sensing platforms usually necessitate the supplementary addition of fluorescent probes,therefore greatly restricting its convenient and broad application.In this study,a highly sensitive and selective ratiometric fluorescence platform for alkaline phosphatase(ALP)detection was established,only employing Prussian blue(PB)nanozymes and a commercially available chromogen of o-phenylenediamine(OPD).PB nanozymes with remarkable peroxidaselike(POD-like)activity can effectively catalyze OPD chromogen to yield 2,3-diaminophenazine(OPDox)with an intense yellow fluorescence at 573 nm emission peak.Target ALP can facilitate ascorbic acid 2-phosphate(AAP)dephosphorylation to generate phosphate and ascorbic acid(AA).Significantly,both these two resultant hydrolysis products could effectively decrease the OPDox generation via a dualpath based inhibition on the PB nanozymes POD-like activity.On the other hand,the generated dehydroascorbic acid(DHAA)from AA oxidation would exclusively react with OPD chromogen to yield3-(dihydroxyethyl)furo[3,4-b]quinoxaline-1-one(DFQ)with a strong blue fluorescent signal at 434nm,which further providing a significant enhancement on the sensing selectivity of ALP detection.As a result,an increased yellow fluorescence of OPDox and decreased blue fluorescence of DFQ could be clearly observed with different ALP addition.A robust linear relationship between the fluorescence ratio of F_(434)/F_(573)and ALP activity ranging from 0.25U/L to 6U/L was obtained,with a low detection limit of 0.112 U/L.This proposed method demonstrates high sensitivity,excellent selectivity,cost-effectiveness,and operational simplicity,yet enabling an effective detection of ALP levels in human serum.展开更多
By the random distribution of metals in a single phase,entropy engineering is applied to construct dense neighboring active centers with diverse electronic and geometric structures,realizing the continuous optimizatio...By the random distribution of metals in a single phase,entropy engineering is applied to construct dense neighboring active centers with diverse electronic and geometric structures,realizing the continuous optimization of multiple primary reactions for oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).Many catalysts developed through entropy engineering have been built in nearly equimolar ratios to pursue high entropy,hindering the identification of the active sites and potentially diluting the concentration of real active sites while weakening their electronic interactions with reaction intermediates.Herein,this work proposes an entropy-engineering strategy in metal nanoparticle-embedded nitrogen carbon electrocatalysts,implemented by entropy-engineered Prussian blue analogs(PBA)as precursors to enhance the catalytic activity of primary Cu-Fe active sites.Through the introduction of the micro-strains driven by entropy engineering,density functional theory(DFT)calculations and geometric phase analysis(GPA)using Lorentz electron microscopy further elucidate the optimization of the adsorption/desorption of intermediates.Furthermore,the multi-dimensional morphology and the size diminishment of the nanocrystals serve to expand the electrochemical area,maximizing the catalytic activity for both ORR and OER.Notably,the Zn-air battery assembled with CuFeCoNiZn-NC operated for over 1300 h with negligible decay.This work presents a paradigm for the design of low-cost electrocatalysts with entropy engineering for multi-step reactions.展开更多
Prussian blue analogues(PBAs)have emerged as highly promising cathode materials for sodium-ion batteries(SIBs)due to their simple synthesis,low cost,structural tunability,and high theoretical capacity.However,despite ...Prussian blue analogues(PBAs)have emerged as highly promising cathode materials for sodium-ion batteries(SIBs)due to their simple synthesis,low cost,structural tunability,and high theoretical capacity.However,despite their significant potential,practical applications of PBAs still face multiple performance limitations.This review provides a comprehensive examination of PBAs structures and their electrochemical reaction mechanisms,and systematically summarizes current synthesis methods and modification strategies,while offering forward-looking insights.Furthermore,from the perspective of industrialization,this review systematically analyzes the synthesis,modification,and core challenges of PBAs by comparatively evaluating the feasibility of different technological pathways based on multiple dimensions,including cost-effectiveness,process scalability,environmental impact,and supply chain security,with the aim of providing forward-looking guidance for bridging the critical gap from lab to market.展开更多
Transition metal oxides(TMOs)have received extensive attention for their unique physical and chemical properties.It is worth noting that Fe-based materials stand out because of their rich natural resources,low toxicit...Transition metal oxides(TMOs)have received extensive attention for their unique physical and chemical properties.It is worth noting that Fe-based materials stand out because of their rich natural resources,low toxicity,low price and other advantages,but at the same time confront with critical challenges such as capacity attenuation and volume expansion.Here,a universal synthesis method of MO/MFe_(2)O_(4)(M=Ni,Cu,Zn)nanomaterials derived from Prussian blue analogues(PBAs)is proposed based on the self-sacrificing template strategy of metal-organic frameworks(MOFs).The calcined products retain the porous structure and small particle size of PBAs,which shorten the ion transport path,provide abundant electroactive sites and void space,effectively alleviate the effect of volume expansion,and improve the reaction kinetics.These MO/MFe_(2)O_(4)anode materials exhibit excellent cyclic reversibility and stability during repeated charge/discharge process,among which,NiO/NiFe_(2)O_(4) shows the best electrochemical performance,retaining a superior specific capacity of 1301.7 mAh g^(-1) following 230 cycles at 0.1 A g^(-1).In addition,the lithium adsorption capacity of the materials was further explored through the calculation of density functional theory(DFT).The research perspectives and strategies reported in this paper have strong universality and offer innovative insights for the synthesis of alternative advanced materials.展开更多
With the rapid development of new energy and the high proportion of new energy connected to the grid,energy storage has become the leading technology driving significant adjustments in the global energy landscape.Elec...With the rapid development of new energy and the high proportion of new energy connected to the grid,energy storage has become the leading technology driving significant adjustments in the global energy landscape.Electrochemical energy storage,as the most popular and promising energy storage method,has received extensive attention.Currently,the most widely used energy storage method is metal-ion secondary batteries,whose performance mainly depends on the cathode material.Prussian blue analogues(PBAs)have a unique open framework structures that allow quick and reversible insertion/extraction of metal ions such as Na^(+),K^(+),Zn^(2+),Li^(+)etc.,thus attracting widespread attention.The advantages of simple synthesis process,abundant resources,and low cost also distinguish it from its counterparts.Unfortunately,the crystal water and structural defects in the PBAs lattice that is generated during the synthesis process,as well as the low Na content,significantly affect their electrochemical performance.This paper focuses on PBAs’synthesis methods,crystal structure,modification strategies,and their potential applications as cathode materials for various metal ion secondary batteries and looks forward to their future development direction.展开更多
To explore high-performance cathode materials for aqueous ammonium ion batteries(AAIBs),vanadium-based Prussian blue analogue composites(VFe-PBAs)were prepared by hydrothermal coprecipitation method to enhance the rev...To explore high-performance cathode materials for aqueous ammonium ion batteries(AAIBs),vanadium-based Prussian blue analogue composites(VFe-PBAs)were prepared by hydrothermal coprecipitation method to enhance the reversible storage of NH_(4)^(+).Benefiting from the stable three-dimensional structure and spacious gap position,VFe-PBAs-2 cathode displays excellent electrochemical activity and rate performance,achieving a high specific capacity of 84.3 mA·h/g at a current density of 1000 mA/g.In addition,VFe-PBAs-2 cathode also shows impressive long-term cycle durability with 85.2% capacity retention after 3×10^(4) cycles at 5000 mA/g.The synthesized cathode materials combined with the high electrochemical activity of vanadium ions significantly promote the rapid transfer of NH_(4)^(+).Furthermore,NH_(4)^(+)embedding/extraction mechanism of VFe-PBAs-2 cathode was revealed by electrochemical kinetics tests and advanced ex-situ characterizations.The experimental results demonstrate that vanadium-modified VFe-PBAs-2 as a cathode material can remarkably improve the capacity,electrochemical activity and cycling stability of AAIBs to achieve high performance NH_(4)^(+)storage.展开更多
Herein,a novel label-free electrochemical immunosensor was fabricated via immobilizing specific anti-β-lactoglobulin(β-LG)antibodies(Abs)onto an integrated electrode of gold nanoparticles(AuNPs)/Prussian blue(PB)/cu...Herein,a novel label-free electrochemical immunosensor was fabricated via immobilizing specific anti-β-lactoglobulin(β-LG)antibodies(Abs)onto an integrated electrode of gold nanoparticles(AuNPs)/Prussian blue(PB)/cubic Ia3d structured mesoporous carbon(CMK-8).This immunosensor allowed for the quantitative detection of the major milk allergenβ-LG.CMK-8 with excellent electrical conductivity and uniformly adjustable pore structure was modified on the glassy carbon electrode(GCE)and served as the sensitive substrate for the electro-polymerization of PB,forming the redox-active layer.AuNPs were subsequently electrochemically deposited on PB/CMK-8/GCE to improve the electrical conductivity and utilized as the connector for Abs immobilization.Duringβ-LG detection,the Abs-modified AuNPs/PB/CMK-8/GCE exhibited a significant reduction in differential pulse voltammetry current signal when exposed toβ-LG,displaying an inverse dose-dependent relationship.The developed electrochemical immunosensor demonstrated good detection performance forβ-LG,with a wider linear range of 0.01-100 ng/mL and a lower detection limit of 4.72 pg/mL.Meanwhile,the sensor exhibited remarkable repeatability,reproducibility,stability and anti-interference capabilities,which was further applied to detectβ-LG in dairy food,achieving satisfactory recoveries(89.2%-98.8%)and lower relative standard deviation(£3.1%).Therefore,this innovative electrochemical method for food allergen detection holds great potential application in food safety determination and evaluation.展开更多
Aqueous zinc-ion batteries(AZIBs)show great potential in the field of electrochemical energy storage with the advantages of high safety,low cost and environmental friendliness.Prussian blue analogues(PBAs)are consider...Aqueous zinc-ion batteries(AZIBs)show great potential in the field of electrochemical energy storage with the advantages of high safety,low cost and environmental friendliness.Prussian blue analogues(PBAs)are considered as the highly promising cathode materials for AZIBs because of their low cost and high voltage potential.Its excellent electrochemical performance and sustainable energy storage capability provide a new direction and opportunity for the development of AZIBs technology.The practical application of PBAs in AZIBs,however,is restrained by its unstable cycle life deriving from PBAs’inherent structure deficiencies and its dissolution in aqueous electrolyte.Based on the summary of series of literature,we will comprehensively introduce the PBAs as cathodes for AZIBs in this review.Firstly,some basic knowledge of PBAs is introduced,including structural characteristics,advantages and issues.Secondly,several commonly used modification methods to improve the properties of PBAs,as well as electrolytes to stabilize PBAs,are presented.Finally,the future research directions and commercial prospects of PBAs in AZIBs are proposed to encourage further exploration and promote technological innovation.展开更多
To meet the current energy needs of society,the highly efficient and continuous production of clean energy is required.One of the key issues facing the green hydrogen evolution is the construction of efficient,low-cos...To meet the current energy needs of society,the highly efficient and continuous production of clean energy is required.One of the key issues facing the green hydrogen evolution is the construction of efficient,low-cost electrocatalysts.Prussian blue(PB),Prussian blue analogs(PBAs),and their derivatives have tunable metal centers and have attracted significant interest as novel photo-and electrochemical catalysts.In this review,recent research progress into PB/PBA-based hollow structures,substrate-supported nanostructures,and their derivatives for green water splitting is discussed and summarized.First,several remarkable examples of nanostructured PB/PBAs supported on substrates(copper foil,carbon cloth,and nickel foam)and hollow structures(such as single-shelled hollow boxes,open hollow cages,and intricate hollow structures(multi-shell and yolk-shell))are discussed in detail,including their synthesis and formation mechanisms.Subsequently,the applications of PB/PBA derivatives((hydr)oxides,phosphides,chalcogenides,and carbides)for water splitting are discussed.Finally,the limitations in this research area and the most urgent challenges are summarized.We hope that this review will stimulate more researchers to develop technologies based on these intricate PB/PBA structures and their derivatives for highly efficient,green water splitting.展开更多
In the applications of large-scale energy storage,aqueous batteries are considered as rivals for organic batteries due to their environmentally friendly and low-cost nature.However,carrier ions always exhibit huge hyd...In the applications of large-scale energy storage,aqueous batteries are considered as rivals for organic batteries due to their environmentally friendly and low-cost nature.However,carrier ions always exhibit huge hydrated radius in aqueous electrolyte,which brings difficulty to find suitable host materials that can achieve highly reversible insertion and extraction of cations.Owing to open threedimensional rigid framework and facile synthesis,Prussian blue analogues(PBAs)receive the most extensive attention among various host candidates in aqueous system.Herein,a comprehensive review on recent progresses of PBAs in aqueous batteries is presented.Based on the application in different aqueous systems,the relationship between electrochemical behaviors(redox potential,capacity,cycling stability and rate performance)and structural characteristics(preparation method,structure type,particle size,morphology,crystallinity,defect,metal atom in highspin state and chemical composition)is analyzed and summarized thoroughly.It can be concluded that the required type of PBAs is different for various carrier ions.In particular,the desalination batteries worked with the same mechanism as aqueous batteries are also discussed in detail to introduce the application of PBAs in aqueous systems comprehensively.This report can help the readers to understand the relationship between physical/chemical characteristics and electrochemical properties for PBAs and find a way to fabricate high-performance PBAs in aqueous batteries and desalination batteries.展开更多
Prussian blue analogue(PBA)material is a promising cathode for applications in Na-ion and K-ion batteries which can support high c-rates for charge and discharge.In this study,the material of composition[K2 CuIIFeII(C...Prussian blue analogue(PBA)material is a promising cathode for applications in Na-ion and K-ion batteries which can support high c-rates for charge and discharge.In this study,the material of composition[K2 CuIIFeII(CN)6]was synthesized and its structural and electrochemical redox behavior was investigated with 5 different alkali insertion cations(Li^+,Na^+,K^+,Rb^+,Cs^+).Galvanostatic measurements indicate that the redox potential strongly depends on the ionic radius of the inserted cation.The redox potential varies by 400 m V between using Li^+(0.79A)or Cs^+(1.73A)in the electrolyte.The underlying modification of the Fe2^+/Fe3^+redox potential in PBA is proposed to be due to the weakening of the Fe–C bond in the material.This hypothesis is supported by XRD measurements which reveal that the lattice parameter of the de-intercalated host structure follows the same trend of monotonic increase with the cation size.The relatively minor volume changes accompanying the redox(1.2%–2.4%)allow the PBA to accommodate differently sized cations,although the structural hindrances are quite pronounced at high c-rates for the larger ones(Rb^+and Cs^+).Cycle aging studies indicate that the minimum capacity fade rate is observed in case of K^+ and Rb^+ containing electrolyte.The peak intensity corresponding to the[220]crystallographic plane varies depending on the state of charge of PBA,since this plane contains the insertion cations.Owing to the sensitivity of the redox potential to the insertion cation coupled with the observed fast ion-exchange ability,the PBA material may find additional analytical applications such as ion sensing or filtration devices.展开更多
Indocyanine green(ICG) is capable of inducing a photothermal effect and the production of cytotoxic reactive oxygen species for cancer therapy. However, the major challenge in applying ICG molecules for antitumor ther...Indocyanine green(ICG) is capable of inducing a photothermal effect and the production of cytotoxic reactive oxygen species for cancer therapy. However, the major challenge in applying ICG molecules for antitumor therapy is associated with their instability in aqueous conditions and rapid clearance from blood circulation,which causes insufficient bioavailability at the tumor site.Herein, we conjugated ICG molecules with Prussian blue nanoparticles enclosing a Fe_3O_4 nanocore, which was facilitated by cationic polyethyleneimine via electrostatic adsorption. The nanocarrier-loaded ICG formed stable aggregates that enhanced cellular uptake and prevented fluorescence quenching. Moreover, the strong superparamagnetism of the Fe_3O_4 core in the obtained nanocomposites further improved cellular internalization of the drugs guided by a localized magnetic field. The therapeutic efficacy of this nanoplatform was evaluated using tumor models established in nude mice, which demonstrated remarkable tumor ablation in vivo due to strong photothermal/photodynamic effects. This study provides promising evidence that this multifunctional nanoagent might function as an efficient mediator for combining photothermal and photodynamic cancer therapy.展开更多
The design of electrode materials with specific structures is considered a promising approach for improving the performance of lithium-ion batteries(LIBs).In this paper,FeO/CoO hollow nanocages coated with a N-doped c...The design of electrode materials with specific structures is considered a promising approach for improving the performance of lithium-ion batteries(LIBs).In this paper,FeO/CoO hollow nanocages coated with a N-doped carbon layer(FCO@NC)was prepared using Fe-Co-based Prussian blue analogs(PBA)as a precursor.During the synthesis,dopamine was the carbon and nitrogen source.The reducing atmosphere was assured via NH_3/Ar,which regulated the vacancies in the structure of FCO@NC as well as increased its conductivity.When used as anode materials for LIBs,the FCO@NC nanocages deliver a high reversible capacity of 774.89 mAh·g^(-1)at 0.3 A·g^(-1)after200 cycles with a capacity retention rate of 80.4%and426.76 mAh·g^(-1)after 500 cycles at a high current density of 1 A·g^(-1).It is demonstrated that the hollow nanocage structure can effectively enhance the cycle stability,and the heat treatment in NH_(3)/Ar atmosphere contributes to the oxygen vacancy content of the electrode materials,further facilitating its conductivity and electrochemical performance.展开更多
Nitric oxide(NO)has emerged as a potential wound therapeutic agent due to its pivotal role in the wound healing processes.Nevertheless,NO-based therapy for clinical applications is still restricted due to its gaseous ...Nitric oxide(NO)has emerged as a potential wound therapeutic agent due to its pivotal role in the wound healing processes.Nevertheless,NO-based therapy for clinical applications is still restricted due to its gaseous state and short half-life.Here we exploited a wound dressing by incorporating sodium nitroprusside doped prussian blue nanoparticals and Type I collagen into the chitosan/poly(vinyl alcohol)nanofibers through the electrospinning method.This hybrid nanofibrous scaffold possess the excellent abilities of NIR controlled NO release,photothermal therapy,and imitation of extra-cellular matrix-like architecture.These synergistic effects could enhance their anti-bactericidal effects in vitro and furthermore accelerate wound healing in vivo when compared to control groups.Histological analysis demonstrated the scaffold could promote fibroblast growth and accelerate epithelialization.Moreover,no apparent histological toxicology and negligible damage to major organs were observed,which provided sufficient biosafety for in vivo application.These data indicate the fabricated hybrid nanofibrous scaffold could be used as an ideal candidate for accelerating wound healing and treating chronic wounds.展开更多
基金financial support from the National Natural Science Foundation of China(NSFC,Grant No.52202253,52372193,and 22293041)Natural Science Foundation of Jiangsu Province(Grant No.BK20220914)Large Instrument and Equipment Sharing Fund of Nanjing University of Aeronautics and Astronautics。
文摘Prussian blue/Prussian blue analogues(PB/PBAs)are widely used in electrochemistry and materials science fields,such as electrochemical energy storage,catalysis,water purification,and electromagnetic wave absorption,owing to their 3D open-framework structure,tunable composition,and large specific surface area.However,the co-precipitation method,which is most suitable for large-scale production of PB/PBAs,often leads to the formation of numerous crystal defects and severe lattice distortion,which significantly affects the structural stability of PB/PBAs.To obtain high-crystallinity PB/PBAs with targeted properties,precise synthesis considering various detailed conditions is especially needed.Herein,this review comprehensively summarizes the fundamental structure composition,key factors in synthesis,and applications in the electrochemistry of PB/PBAs.Unlike previous reports,this review elucidates the relationship between the physicochemical properties of PB/PBAs and their structural composition,with a particular focus on revealing the mechanisms and significance of specific preparation methods during the synthesis process,including reactant concentration,chelating agent,aging,atmosphere,temperature,and drying conditions,for achieving the precise fabrication of PB/PBAs nanomaterials.As PB/PBAs gradually become materials for multidimensional applications,we urge greater attention to the unique properties of PB/PBAs that are sustained by high crystallinity and stable crystal structures.This will effectively ensure the maximization of their advantages in practical applications.
基金financial support from the Special Funds for the Cultivation of Guangdong College Students’Scientific and Technological Innovation(“Climbing Program”Special Funds,pdjh2023b0145)the Scientific Research Innovation Project of Graduate School of South China Normal University(2024KYLX047)financial support from the Australian Research Council,Centre for Materials Science,Queensland University of Technology.
文摘Lithium-ion batteries(LIBs)have dominated the portable electronic and electrochemical energy markets since their commercialisation,whose high cost and lithium scarcity have prompted the development of other alkali-ion batteries(AIBs)including sodium-ion batteries(SIBs)and potassium-ion batteries(PIBs).Owing to larger ion sizes of Na^(+)and K^(+)compared with Li^(+),nanocomposites with excellent crystallinity orientation and well-developed porosity show unprecedented potential for advanced lithium/sodium/potassium storage.With enticing open rigid framework structures,Prussian blue analogues(PBAs)remain promising self-sacrificial templates for the preparation of various nanocomposites,whose appeal originates from the well-retained porous structures and exceptional electrochemical activities after thermal decomposition.This review focuses on the recent progress of PBA-derived nanocomposites from their fabrication,lithium/sodium/potassium storage mechanism,and applications in AIBs(LIBs,SIBs,and PIBs).To distinguish various PBA derivatives,the working mechanism and applications of PBA-templated metal oxides,metal chalcogenides,metal phosphides,and other nanocomposites are systematically evaluated,facilitating the establishment of a structure–activity correlation for these materials.Based on the fruitful achievements of PBA-derived nanocomposites,perspectives for their future development are envisioned,aiming to narrow down the gap between laboratory study and industrial reality.
基金financially supported by research grants from Innovative Research Group Project of National Natural Science Foundation of China(No.52021004)National Key Research and Development Program of China(2022YFB3803300)+2 种基金National Natural Science Foundation of China(62474026 and 62074022)Natural Science Foundation of Chongqing(CSTB2024NSCQ-MSX1215,cstc2021jcyj-jqX0015 and CSTB2022NSCQ-MSX1183)the Youth Talent Support Program of Chongqing(CQYC2021059206).
文摘ⅢThe superior adaptability of Prussian blue analogues(PBAs)in interacting with potassium ions has shifted research focus toward their potential application as cathodes of potassium-ion batteries(PIBs).The large interstitial space formed between metal ions and–C≡N–in PBAs can accommodate large-radius K^(+).However,the rapid nucleation in the co-precipitation synthesis process of PBAs induces many lattice defects of[M(CN)_(6)]^(4-)vacancies(V_([M–C≡N])),interstitial and coordinated H_(2)O molecules,which will directly lead to performance degradation.Moreover,originating from various transition metal elements in low/high-spin electron configuration states,PBAs exhibit diverse electrochemical behaviors,such as low reaction kinetics of low-spin iron(Ⅱ),Jahn-Teller distortion and dissolution of manganese(Ⅲ),and electrochemical inertness of nickel(Ⅱ)and copper(Ⅱ).Here,we summarize recently reported structures and properties of PBAs,classifying them based on the types of transition metals(iron,cobalt,manganese,copper,nickel)employed.Advanced synthesis strategies,including control engineering of crystallinity based on H_(2)O molecules and V_([M–C≡N]),were discussed.Also,the approaches for enhancing the electrochemical performance of PBAs were highlighted.Finally,the challenges and prospects towards the future development of PBAs are put forward.The review is expected to provide technical and theoretical support for the design of high-performance PBAs.
基金funding support from the Macao Science and Technology Development Fund(0013/2021/AMJ and 0082/2022/A2)support from the Multi-Year Research Grants(MYRG2022-00266-IAPME,and MYRG-GRG2023-00224-IAPME)provided by the Research&Development Office at the University of Macao+2 种基金the National Natural Science Foundation of China(52202328)the Shanghai Sailing Program(22YF1455500)the Shanghai Magnolia Talent Plan Pujiang Project(24PJD128)for their financial support。
文摘Iron-based Prussian white(PW)materials have attracted considerable attention as promising cathodes for potassium-ion batteries(PIBs)due to their high capacity,easy preparation,and economic merits.However,the intrinsic iron dissolution and uncontrollable cathode-electrolyte interface(CEI)formation in conventional organic electrolytes severely hinder their long-term cycling stability.Herein,we employ succinonitrile(SN),a bifunctional electrolyte additive,to suppress the iron dissolution and promote thin,uniform,and stable CEI formation of the PW cathode,thus improving its structural stability.Benefited from the coordination between the cyano groups in SN and iron atoms,this molecule can preferentially adsorb on the surface of PW to mitigate iron dissolution.SN also facilitates the decomposition of anions in potassium salt rather than organic solvents in electrolyte due to the attractive reaction between SN and anions.Consequently,the PW cathode with SN additive provides better electrochemical reversibility,showing capacity retention of 93.6%after 3000 cycles at 5C.In comparison,without SN,the capacity retention is only 87.4%after 1000 cycles under the same conditions.Moreover,the full cells of PW matched with commercial graphite(Gr)achieve stable cycling for 3500 cycles at a high rate of 20C,with an exceptional capacity decay of only 0.005%per cycle,surpassing the majority of recently reported results in literature.
基金supported by the Key Reasearch and Development Program of Zhejiang(2022C01029)the National Natural Science Foundation of China(22225802 and 22288102)the Research Funds of Institute of Zhejiang University-Quzhou(IZQ2022KJ3005).
文摘The removal of cesium-137(^(137)Cs)from nuclear wastewater remains crucial due to its radioactivity and high solubility in water,which pose serious risk to human health and the environment.Aiming at selective capture of Cs^(+) from wastewater,a core-shell adsorbent,Prussian blue analog@y-alumina(PBA@Al_(2)O_(3))pellets were synthesized using the hydrothermal-stepwise deposition method.The coreshell PBA@Al_(2)O_(3)pellets showcased a PBA loading of 25%and demonstrated a maximum adsorption capacity of 15.65 mg·g^(-1).The adsorption data was consistent with the pseudo-second-order kinetic model and the Langmuir isotherm model.It effectively reduced bulk Cs^(+) concentrations from an initial 6.62 mg·L^(-1)to 2 μg·L^(-1),achieving a removal efficiency of 99.97%and distribution coefficient(Kd)of 1.265×10^(6)ml·g^(-1),surpassing the performance of other PBA-based materials.The material also indicated good mechanical properties and cesium ion removal rates of 99.7%across a wide pH range(1.82 to 11.12).Furthermore,PBA@Al_(2)O_(3)exhibited consistent removal rate of over 99%and good selectivity(SF=50-1600)towards Cs^(+) even in the presence of interfering ions such as Na^(+),K^(+),Mg^(2+),and Ca^(2+)ions.The Kd(Cs^(+))for PBA@Al2O3 in simulated seawater and groundwater were 9.92×10^(3)and 2.23×10^(4)ml·g^(-1),where the removal rates reached 96.1%and 98.2%,respectively.XPS confirms that the adsorption mechanism is the ion exchange between Cs^(+) and K^(+)ions.This study underscores the significant potential of inorganic core-shell pellets adsorbents as promising agents for the selective capture of Cs^(+) from wastewater.
基金supported by the National Natural Science Foundation of China(52203257)Natural Science Foundation of Heilongjiang Province(YQ2022B008).
文摘Bimetallic oxides are promising electrocatalysts due to their rich composition,facile synthesis,and favorable stability under oxidizing conditions.This paper innovatively proposes a strategy aimed at constructing a one-dimensional heterostructure(Fe–NiO/NiMoO_(4) nanoparticles/nanofibers).The strategy commences with the meticulous treatment of NiMoO_(4) nanofibers,utilizing in situ etching techniques to induce the formation of Prussian Blue Analog compounds.In this process,[Fe(CN)_(6)]^(3-)anions react with the NiMoO_(4) host layer to form a steady NiFe PBA.Subsequently,the surface/interface reconstituted NiMoO_(4) nanofibers undergo direct oxidation,leading to a reconfiguration of the surface structure and the formation of a unique Fe–NiO/NiMoO_(4) one-dimensional heterostructure.The catalyst showed markedly enhanced electrocatalytic performance for the oxygen evolution reaction.Density functional theory results reveal that the incorporation of Fe as a dopant dramatically reduces the Gibbs free energy associated with the rate-determining step in the oxygen evolution reaction pathway.This pivotal transformation directly lowers the activation energy barrier,thereby significantly enhancing electron transfer efficiency.
基金supported by the National Natural Science Foundation of China(No.22064014)the Science and Technology Development Plan Project of Lanzhou(No.2021–1-146)+2 种基金the Science and Technology Project of Gansu Province(Nos.21YF5FA071,21JR7RA538)the Industrial Support Programme for Higher Education Institutions Project(Nos.2023CYZC-69,2024CYCZ-05)the 2023 Gansu Provincial Key Talent Project(No.2023RCXM26)。
文摘The traditional nanozymes-based ratiometric fluorescence sensing platforms usually necessitate the supplementary addition of fluorescent probes,therefore greatly restricting its convenient and broad application.In this study,a highly sensitive and selective ratiometric fluorescence platform for alkaline phosphatase(ALP)detection was established,only employing Prussian blue(PB)nanozymes and a commercially available chromogen of o-phenylenediamine(OPD).PB nanozymes with remarkable peroxidaselike(POD-like)activity can effectively catalyze OPD chromogen to yield 2,3-diaminophenazine(OPDox)with an intense yellow fluorescence at 573 nm emission peak.Target ALP can facilitate ascorbic acid 2-phosphate(AAP)dephosphorylation to generate phosphate and ascorbic acid(AA).Significantly,both these two resultant hydrolysis products could effectively decrease the OPDox generation via a dualpath based inhibition on the PB nanozymes POD-like activity.On the other hand,the generated dehydroascorbic acid(DHAA)from AA oxidation would exclusively react with OPD chromogen to yield3-(dihydroxyethyl)furo[3,4-b]quinoxaline-1-one(DFQ)with a strong blue fluorescent signal at 434nm,which further providing a significant enhancement on the sensing selectivity of ALP detection.As a result,an increased yellow fluorescence of OPDox and decreased blue fluorescence of DFQ could be clearly observed with different ALP addition.A robust linear relationship between the fluorescence ratio of F_(434)/F_(573)and ALP activity ranging from 0.25U/L to 6U/L was obtained,with a low detection limit of 0.112 U/L.This proposed method demonstrates high sensitivity,excellent selectivity,cost-effectiveness,and operational simplicity,yet enabling an effective detection of ALP levels in human serum.
基金supported by the National Natural Science Foundation of China(52071083,52231007,12327804,52471224)Zhuhai Fudan Innovation Institute,and the Science and Technology Commission of Shanghai Municipality(23ZR1405000).
文摘By the random distribution of metals in a single phase,entropy engineering is applied to construct dense neighboring active centers with diverse electronic and geometric structures,realizing the continuous optimization of multiple primary reactions for oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).Many catalysts developed through entropy engineering have been built in nearly equimolar ratios to pursue high entropy,hindering the identification of the active sites and potentially diluting the concentration of real active sites while weakening their electronic interactions with reaction intermediates.Herein,this work proposes an entropy-engineering strategy in metal nanoparticle-embedded nitrogen carbon electrocatalysts,implemented by entropy-engineered Prussian blue analogs(PBA)as precursors to enhance the catalytic activity of primary Cu-Fe active sites.Through the introduction of the micro-strains driven by entropy engineering,density functional theory(DFT)calculations and geometric phase analysis(GPA)using Lorentz electron microscopy further elucidate the optimization of the adsorption/desorption of intermediates.Furthermore,the multi-dimensional morphology and the size diminishment of the nanocrystals serve to expand the electrochemical area,maximizing the catalytic activity for both ORR and OER.Notably,the Zn-air battery assembled with CuFeCoNiZn-NC operated for over 1300 h with negligible decay.This work presents a paradigm for the design of low-cost electrocatalysts with entropy engineering for multi-step reactions.
基金supported by the National Natural Science Foundation of China(NSFC)(No.52301257,62475003)the Beijing Natural Science Foundation(No.2252031)。
文摘Prussian blue analogues(PBAs)have emerged as highly promising cathode materials for sodium-ion batteries(SIBs)due to their simple synthesis,low cost,structural tunability,and high theoretical capacity.However,despite their significant potential,practical applications of PBAs still face multiple performance limitations.This review provides a comprehensive examination of PBAs structures and their electrochemical reaction mechanisms,and systematically summarizes current synthesis methods and modification strategies,while offering forward-looking insights.Furthermore,from the perspective of industrialization,this review systematically analyzes the synthesis,modification,and core challenges of PBAs by comparatively evaluating the feasibility of different technological pathways based on multiple dimensions,including cost-effectiveness,process scalability,environmental impact,and supply chain security,with the aim of providing forward-looking guidance for bridging the critical gap from lab to market.
文摘Transition metal oxides(TMOs)have received extensive attention for their unique physical and chemical properties.It is worth noting that Fe-based materials stand out because of their rich natural resources,low toxicity,low price and other advantages,but at the same time confront with critical challenges such as capacity attenuation and volume expansion.Here,a universal synthesis method of MO/MFe_(2)O_(4)(M=Ni,Cu,Zn)nanomaterials derived from Prussian blue analogues(PBAs)is proposed based on the self-sacrificing template strategy of metal-organic frameworks(MOFs).The calcined products retain the porous structure and small particle size of PBAs,which shorten the ion transport path,provide abundant electroactive sites and void space,effectively alleviate the effect of volume expansion,and improve the reaction kinetics.These MO/MFe_(2)O_(4)anode materials exhibit excellent cyclic reversibility and stability during repeated charge/discharge process,among which,NiO/NiFe_(2)O_(4) shows the best electrochemical performance,retaining a superior specific capacity of 1301.7 mAh g^(-1) following 230 cycles at 0.1 A g^(-1).In addition,the lithium adsorption capacity of the materials was further explored through the calculation of density functional theory(DFT).The research perspectives and strategies reported in this paper have strong universality and offer innovative insights for the synthesis of alternative advanced materials.
基金supported by the National Natural Science Foundation of China(No.52072217)the National Key Research and Development Program of China(No.2022YFB3807700)+2 种基金the Joint Funds of the Hubei Natural Science Foundation Innovation and Development(No.2022CFD034)Hubei Natural Science Foundation Innovation Group Project(No.2022CFA020)the Major Technological Innovation Project of Hubei Science and Technology Department(No.2019AAA164).
文摘With the rapid development of new energy and the high proportion of new energy connected to the grid,energy storage has become the leading technology driving significant adjustments in the global energy landscape.Electrochemical energy storage,as the most popular and promising energy storage method,has received extensive attention.Currently,the most widely used energy storage method is metal-ion secondary batteries,whose performance mainly depends on the cathode material.Prussian blue analogues(PBAs)have a unique open framework structures that allow quick and reversible insertion/extraction of metal ions such as Na^(+),K^(+),Zn^(2+),Li^(+)etc.,thus attracting widespread attention.The advantages of simple synthesis process,abundant resources,and low cost also distinguish it from its counterparts.Unfortunately,the crystal water and structural defects in the PBAs lattice that is generated during the synthesis process,as well as the low Na content,significantly affect their electrochemical performance.This paper focuses on PBAs’synthesis methods,crystal structure,modification strategies,and their potential applications as cathode materials for various metal ion secondary batteries and looks forward to their future development direction.
基金supported by the National Natural Science Foundation of China(No.52374301)the Hebei Provincial Natural Science Foundation,China(No.E2024501010)+2 种基金the Shijiazhuang Basic Research Project,China(No.241790667A)the Fundamental Research Funds for the Central Universities,China(No.N2423054)the Performance Subsidy Fund for Key Laboratory of Dielectric and Electrolyte Functional Material of Hebei Province,China(No.22567627H).
文摘To explore high-performance cathode materials for aqueous ammonium ion batteries(AAIBs),vanadium-based Prussian blue analogue composites(VFe-PBAs)were prepared by hydrothermal coprecipitation method to enhance the reversible storage of NH_(4)^(+).Benefiting from the stable three-dimensional structure and spacious gap position,VFe-PBAs-2 cathode displays excellent electrochemical activity and rate performance,achieving a high specific capacity of 84.3 mA·h/g at a current density of 1000 mA/g.In addition,VFe-PBAs-2 cathode also shows impressive long-term cycle durability with 85.2% capacity retention after 3×10^(4) cycles at 5000 mA/g.The synthesized cathode materials combined with the high electrochemical activity of vanadium ions significantly promote the rapid transfer of NH_(4)^(+).Furthermore,NH_(4)^(+)embedding/extraction mechanism of VFe-PBAs-2 cathode was revealed by electrochemical kinetics tests and advanced ex-situ characterizations.The experimental results demonstrate that vanadium-modified VFe-PBAs-2 as a cathode material can remarkably improve the capacity,electrochemical activity and cycling stability of AAIBs to achieve high performance NH_(4)^(+)storage.
基金supported by the National Natural Science Foundation of China(32272416,31972147)Project of Tianjin Science and Technology Plan(22ZYJDSS00030).
文摘Herein,a novel label-free electrochemical immunosensor was fabricated via immobilizing specific anti-β-lactoglobulin(β-LG)antibodies(Abs)onto an integrated electrode of gold nanoparticles(AuNPs)/Prussian blue(PB)/cubic Ia3d structured mesoporous carbon(CMK-8).This immunosensor allowed for the quantitative detection of the major milk allergenβ-LG.CMK-8 with excellent electrical conductivity and uniformly adjustable pore structure was modified on the glassy carbon electrode(GCE)and served as the sensitive substrate for the electro-polymerization of PB,forming the redox-active layer.AuNPs were subsequently electrochemically deposited on PB/CMK-8/GCE to improve the electrical conductivity and utilized as the connector for Abs immobilization.Duringβ-LG detection,the Abs-modified AuNPs/PB/CMK-8/GCE exhibited a significant reduction in differential pulse voltammetry current signal when exposed toβ-LG,displaying an inverse dose-dependent relationship.The developed electrochemical immunosensor demonstrated good detection performance forβ-LG,with a wider linear range of 0.01-100 ng/mL and a lower detection limit of 4.72 pg/mL.Meanwhile,the sensor exhibited remarkable repeatability,reproducibility,stability and anti-interference capabilities,which was further applied to detectβ-LG in dairy food,achieving satisfactory recoveries(89.2%-98.8%)and lower relative standard deviation(£3.1%).Therefore,this innovative electrochemical method for food allergen detection holds great potential application in food safety determination and evaluation.
基金financially supported by the National Natural Science Foundation of China(Youth Program,Nos.52204378 and No.22309209)the Natural Science Foundation of Hunan Province in China(No.2023JJ40709).
文摘Aqueous zinc-ion batteries(AZIBs)show great potential in the field of electrochemical energy storage with the advantages of high safety,low cost and environmental friendliness.Prussian blue analogues(PBAs)are considered as the highly promising cathode materials for AZIBs because of their low cost and high voltage potential.Its excellent electrochemical performance and sustainable energy storage capability provide a new direction and opportunity for the development of AZIBs technology.The practical application of PBAs in AZIBs,however,is restrained by its unstable cycle life deriving from PBAs’inherent structure deficiencies and its dissolution in aqueous electrolyte.Based on the summary of series of literature,we will comprehensively introduce the PBAs as cathodes for AZIBs in this review.Firstly,some basic knowledge of PBAs is introduced,including structural characteristics,advantages and issues.Secondly,several commonly used modification methods to improve the properties of PBAs,as well as electrolytes to stabilize PBAs,are presented.Finally,the future research directions and commercial prospects of PBAs in AZIBs are proposed to encourage further exploration and promote technological innovation.
文摘To meet the current energy needs of society,the highly efficient and continuous production of clean energy is required.One of the key issues facing the green hydrogen evolution is the construction of efficient,low-cost electrocatalysts.Prussian blue(PB),Prussian blue analogs(PBAs),and their derivatives have tunable metal centers and have attracted significant interest as novel photo-and electrochemical catalysts.In this review,recent research progress into PB/PBA-based hollow structures,substrate-supported nanostructures,and their derivatives for green water splitting is discussed and summarized.First,several remarkable examples of nanostructured PB/PBAs supported on substrates(copper foil,carbon cloth,and nickel foam)and hollow structures(such as single-shelled hollow boxes,open hollow cages,and intricate hollow structures(multi-shell and yolk-shell))are discussed in detail,including their synthesis and formation mechanisms.Subsequently,the applications of PB/PBA derivatives((hydr)oxides,phosphides,chalcogenides,and carbides)for water splitting are discussed.Finally,the limitations in this research area and the most urgent challenges are summarized.We hope that this review will stimulate more researchers to develop technologies based on these intricate PB/PBA structures and their derivatives for highly efficient,green water splitting.
基金This work was sponsored by NSAF Joint Fund(U1830106)Science and Technology Innovation 2025 Major Program of Ningbo(2018B10061)K.C.Wong Magna Fund in Ningbo University.
文摘In the applications of large-scale energy storage,aqueous batteries are considered as rivals for organic batteries due to their environmentally friendly and low-cost nature.However,carrier ions always exhibit huge hydrated radius in aqueous electrolyte,which brings difficulty to find suitable host materials that can achieve highly reversible insertion and extraction of cations.Owing to open threedimensional rigid framework and facile synthesis,Prussian blue analogues(PBAs)receive the most extensive attention among various host candidates in aqueous system.Herein,a comprehensive review on recent progresses of PBAs in aqueous batteries is presented.Based on the application in different aqueous systems,the relationship between electrochemical behaviors(redox potential,capacity,cycling stability and rate performance)and structural characteristics(preparation method,structure type,particle size,morphology,crystallinity,defect,metal atom in highspin state and chemical composition)is analyzed and summarized thoroughly.It can be concluded that the required type of PBAs is different for various carrier ions.In particular,the desalination batteries worked with the same mechanism as aqueous batteries are also discussed in detail to introduce the application of PBAs in aqueous systems comprehensively.This report can help the readers to understand the relationship between physical/chemical characteristics and electrochemical properties for PBAs and find a way to fabricate high-performance PBAs in aqueous batteries and desalination batteries.
基金“Le Studium Loire Valley Institute for Advanced Studies” for financial and logistical support to the researchers involved in this study“Region Centre” for financial support under the “Lavoisier” program
文摘Prussian blue analogue(PBA)material is a promising cathode for applications in Na-ion and K-ion batteries which can support high c-rates for charge and discharge.In this study,the material of composition[K2 CuIIFeII(CN)6]was synthesized and its structural and electrochemical redox behavior was investigated with 5 different alkali insertion cations(Li^+,Na^+,K^+,Rb^+,Cs^+).Galvanostatic measurements indicate that the redox potential strongly depends on the ionic radius of the inserted cation.The redox potential varies by 400 m V between using Li^+(0.79A)or Cs^+(1.73A)in the electrolyte.The underlying modification of the Fe2^+/Fe3^+redox potential in PBA is proposed to be due to the weakening of the Fe–C bond in the material.This hypothesis is supported by XRD measurements which reveal that the lattice parameter of the de-intercalated host structure follows the same trend of monotonic increase with the cation size.The relatively minor volume changes accompanying the redox(1.2%–2.4%)allow the PBA to accommodate differently sized cations,although the structural hindrances are quite pronounced at high c-rates for the larger ones(Rb^+and Cs^+).Cycle aging studies indicate that the minimum capacity fade rate is observed in case of K^+ and Rb^+ containing electrolyte.The peak intensity corresponding to the[220]crystallographic plane varies depending on the state of charge of PBA,since this plane contains the insertion cations.Owing to the sensitivity of the redox potential to the insertion cation coupled with the observed fast ion-exchange ability,the PBA material may find additional analytical applications such as ion sensing or filtration devices.
基金financial support from Fundamental Research Funds for Central Universities (XDJK2016A010 and XDJK2017C001)National Natural Science Foundation of China (51703186 and 31671037)Southwest University (SWU116032 and SWU115059)
文摘Indocyanine green(ICG) is capable of inducing a photothermal effect and the production of cytotoxic reactive oxygen species for cancer therapy. However, the major challenge in applying ICG molecules for antitumor therapy is associated with their instability in aqueous conditions and rapid clearance from blood circulation,which causes insufficient bioavailability at the tumor site.Herein, we conjugated ICG molecules with Prussian blue nanoparticles enclosing a Fe_3O_4 nanocore, which was facilitated by cationic polyethyleneimine via electrostatic adsorption. The nanocarrier-loaded ICG formed stable aggregates that enhanced cellular uptake and prevented fluorescence quenching. Moreover, the strong superparamagnetism of the Fe_3O_4 core in the obtained nanocomposites further improved cellular internalization of the drugs guided by a localized magnetic field. The therapeutic efficacy of this nanoplatform was evaluated using tumor models established in nude mice, which demonstrated remarkable tumor ablation in vivo due to strong photothermal/photodynamic effects. This study provides promising evidence that this multifunctional nanoagent might function as an efficient mediator for combining photothermal and photodynamic cancer therapy.
基金financially supported by the National Natural Science Foundation of China (No.52274294)the Fundamental Research Funds for the Central Universities (No.N2124007-1)。
文摘The design of electrode materials with specific structures is considered a promising approach for improving the performance of lithium-ion batteries(LIBs).In this paper,FeO/CoO hollow nanocages coated with a N-doped carbon layer(FCO@NC)was prepared using Fe-Co-based Prussian blue analogs(PBA)as a precursor.During the synthesis,dopamine was the carbon and nitrogen source.The reducing atmosphere was assured via NH_3/Ar,which regulated the vacancies in the structure of FCO@NC as well as increased its conductivity.When used as anode materials for LIBs,the FCO@NC nanocages deliver a high reversible capacity of 774.89 mAh·g^(-1)at 0.3 A·g^(-1)after200 cycles with a capacity retention rate of 80.4%and426.76 mAh·g^(-1)after 500 cycles at a high current density of 1 A·g^(-1).It is demonstrated that the hollow nanocage structure can effectively enhance the cycle stability,and the heat treatment in NH_(3)/Ar atmosphere contributes to the oxygen vacancy content of the electrode materials,further facilitating its conductivity and electrochemical performance.
基金NNSFC(21901186,82004163)NSF of Shandong Province(ZR2019BB032,ZR2020MH400,ZR2020QH324)for financial support。
文摘Nitric oxide(NO)has emerged as a potential wound therapeutic agent due to its pivotal role in the wound healing processes.Nevertheless,NO-based therapy for clinical applications is still restricted due to its gaseous state and short half-life.Here we exploited a wound dressing by incorporating sodium nitroprusside doped prussian blue nanoparticals and Type I collagen into the chitosan/poly(vinyl alcohol)nanofibers through the electrospinning method.This hybrid nanofibrous scaffold possess the excellent abilities of NIR controlled NO release,photothermal therapy,and imitation of extra-cellular matrix-like architecture.These synergistic effects could enhance their anti-bactericidal effects in vitro and furthermore accelerate wound healing in vivo when compared to control groups.Histological analysis demonstrated the scaffold could promote fibroblast growth and accelerate epithelialization.Moreover,no apparent histological toxicology and negligible damage to major organs were observed,which provided sufficient biosafety for in vivo application.These data indicate the fabricated hybrid nanofibrous scaffold could be used as an ideal candidate for accelerating wound healing and treating chronic wounds.