Progress on Transition Metal Ions Dissolution Suppression Strategies in Prussian Blue Analogs for Aqueous Sodium-/Potassium-Ion Batteries

Aqueous sodium-ion batteries(ASIBs)and aqueous potassium-ion batteries(APIBs)present significant potential for large-scale energy storage due to their cost-effectiveness,safety,and environmental compatibility.Nonetheless,the intricate energy storage mechanisms in aqueous electrolytes place stringent require-ments on the host materials.Prussian blue analogs(PBAs),with their open three-dimensional framework and facile synthesis,stand out as leading candidates for aqueous energy storage.However,PBAs possess a swift capacity fade and limited cycle longevity,for their structural integrity is compromised by the pronounced dis-solution of transition metal(TM)ions in the aqueous milieu.This manuscript provides an exhaustive review of the recent advancements concerning PBAs in ASIBs and APIBs.The dissolution mechanisms of TM ions in PBAs,informed by their structural attributes and redox processes,are thoroughly examined.Moreover,this study delves into innovative design tactics to alleviate the dissolution issue of TM ions.In conclusion,the paper consolidates various strategies for suppressing the dissolution of TM ions in PBAs and posits avenues for prospective exploration of high-safety aqueous sodium-/potassium-ion batteries.

Asymmetric Electrolytes Design for Aqueous Multivalent Metal Ion Batteries

With the rapid development of portable electronics and electric road vehicles,high-energy-density batteries have been becoming front-burner issues.Traditionally,homogeneous electrolyte cannot simultaneously meet diametrically opposed demands of high-potential cathode and low-potential anode,which are essential for high-voltage batteries.Meanwhile,homogeneous electrolyte is difficult to achieve bi-or multi-functions to meet different requirements of electrodes.In comparison,the asymmetric electrolyte with bi-or multi-layer disparate components can satisfy distinct requirements by playing different roles of each electrolyte layer and meanwhile compensates weakness of individual electrolyte.Consequently,the asymmetric electrolyte can not only suppress by-product sedimentation and continuous electrolyte decomposition at the anode while preserving active substances at the cathode for high-voltage batteries with long cyclic lifespan.In this review,we comprehensively divide asymmetric electrolytes into three categories:decoupled liquid-state electrolytes,bi-phase solid/liquid electrolytes and decoupled asymmetric solid-state electrolytes.The design principles,reaction mechanism and mutual compatibility are also studied,respectively.Finally,we provide a comprehensive vision for the simplification of structure to reduce costs and increase device energy density,and the optimization of solvation structure at anolyte/catholyte interface to realize fast ion transport kinetics.

Effects of heavy metal ions Cu^(2+)/Pb^(2+)/Zn^(2+)on kinetic rate constants of struvite crystallization

Struvite(MAP)crystallization technology is widely used to treat ammonia nitrogen in waste effluents of its simple operation and good removal efficiency.However,the presence of heavy metal ions in the waste effluents causes problems such as slow crystallization rate and small crystal size,limiting the recovery rate and economic value of the MAP.The present study was conducted to investigate the effects of concentrations of three heavy metal ions(Cu^(2+),Zn^(2+),and Pb^(2+))on the crystal morphology,crystal size,average growth rate,and crystallization kinetics of MAP.A relationship was established between the kinetic rate constant Ktcalculated by the chemical gradient model and the concentrations of heavy metal ions.The results showed that low concentrations of heavy metal ions in the solution created pits on the MAP surface,and high level of heavy metal ions generated flocs on the MAP surface,which were composed of metal hydroxides,thus inhibiting crystal growth.The crystal size,average growth rate,MAP crystallization rate,and kinetic rate constant Ktdecreased with the increase in heavy metal ion concentration.Moreover,the Ktdemonstrated a linear relationship with the heavy metal concentration ln(C/C~*),which provided a reference for the optimization of the MAP crystallization process in the presence of heavy metal ions.

Dual-functional pyrene implemented mesoporous silicon material used for the detection and adsorption of metal ions

A fluorescent active organic–inorganic hybrid material Py N-SBA-15 was synthesized by implementing pyrene derivatives into mesoporous SBA-15 silica.Py N-SBA-15 had detection and removal functionalities toward Al^(3+),Cu^(2+),and Hg^(2+).On the one hand,Py N-SBA-15 was used as a fluorescence sensor and displayed high sensitivity toward Al^(3+),Cu^(2+),and Hg^(2+)cations (limit of detection:8.0×10^(-7),1.1×10^(-7),and 2.9×10^(-6)mol·L^(–1),respectively) among various analytes with“turn-off”response.On the other hand,the adsorption studies for these toxic analytes (Cu^(2+),Hg^(2+),and Al^(3+)) showed that the ion removal capacity could reach up to 45,581,and 85 mg·g^(-1),respectively.Moreover,the Langmuir isotherm models were better fitted with the adsorption data,indicating that the adsorption was mono-layer adsorption.Kinetic analysis revealed that the adsorption process was well described by the pseudo-second-order kinetic model for Cu^(2+)and Hg^(2+)and pseudo-first-order kinetic model for Al^(3+).The prepared silica material could be reused in four recycles without significantly decreasing its adsorption capacity.Therefore,the Py N-SBA-15 material can serve as a promising candidate for the simultaneous rapid detection and efficient adsorption of metal ions.

Revealing alkali metal ions transport mechanism in the atomic channels of Au@a-MnO_(2)

Understanding alkali metal ions’(e.g.,Li^(+)/Na^(+)/K^(+))transport mechanism is challenging but critical to improving the performance of alkali metal batteries.Herein using a-MnO_(2)nanowires as cathodes,the transport kinetics of Li^(+)/Na^(+)/K^(+)in the 2×2 channels of a-MnO_(2)with a growth direction of[001]is revealed.We show that ion radius plays a decisive role in determining the ion transport and electrochemistry.Regardless of the ion radii,Li^(+)/Na^(+)/K^(+)can all go through the 2×2 channels of a-MnO_(2),generating large stress and causing channel merging or opening.However,smaller ions such as Li^(+)and Na^(+)cannot only transport along the[001]direction but also migrate along the<110>direction to the nanowire surface;for large ion such as K^(+),diffusion along the<110>direction is prohibited.The different ion transport behavior has grand consequences in the electrochemistry of metal oxygen batteries(MOBs).For Li-O_(2)battery,Li^(+)transports uniformly to the nanowire surface,forming a uniform layer of oxide;Na^(+)also transports to the nanowire surface but may be clogged locally due to its larger radius,therefore sporadic pearl-like oxides form on the nanowire surface;K^(+)cannot transport to the nanowire surface due to its large radius,instead,it breaks the nanowire locally,causing local deposition of potassium oxides.The study provides atomic scale understanding of the alkali metal ion transport mechanism which may be harnessed to improve the performance of MOBs.

Effect of mono-/divalent metal ions on the conductivity characteristics of DNA solutions transferring through a microfluidic channel

Interactions between deoxyribonucleic acid(DNA) and metal ions are vital for maintaining life functions, however,there are still unsolved questions about its mechanisms. It is of great practical significance to study these issues for medical chip design, drug development, health care, etc. In this investigation, the conductivity properties of λ-DNA solutions with mono-/divalent metal ions(Na+, K^(+), Mg^(2+), and Ca^(2+)) are experimentally studied as they are electrically driven through a 5 μm microfluidic channel. Experimental data indicate that the conductivities of λ-DNA solutions with metal ions(M+/M2+) basically tend to reduce firstly and then increase as the voltage increases, of which the turning points varied with the metal ions. When the voltage surpasses turning points, the conductivity of λ-DNA-M+solutions increases with the concentration of metal ions, while that of λ-DNA-M^(2+)solutions decrease. Moreover, the conductivity of λ-DNA-M^(2+)solutions is always smaller than that of λ-DNA-M+solutions, and with high-concentration M^(2+), it is even smaller than that of the λ-DNA solution. The main reasons for the above findings could be attributed to the polarization of electrodes and different mechanisms of interactions between metal ions and λ-DNA molecules. This investigation is helpful for the precise manipulation of single DNA molecules in micro-/nanofluidic space and the design of new biomedical micro-/nanofluidic sensors.

Metal ions as effectual tools for cancer with traditional Chinese medicine

Malignant tumor has become a major threat affecting human health,and is one of the main causes of human death.Recent studies have shown that many traditional Chinese medicines(TCM)have good anti-tumor activity,which may improve the therapeutic effect of routine treatment and quality of life with lower toxicity.However,the efficacy of TCM alone for the treatment of tumors is limited.Metal ions are essential substances for maintaining normal physiological activities.This article summarized the multiple mechanisms in which metal ions are involved in the prevention and treatment of tumors in TCM.

Synthesis and Characteristics of A Novel Heavy Metal Ions Chelator

Polyacrylamide-urea-sulfanilamide（PUS） was prepared as a novel heavy metal ions chelator and successfully used to simultaneously remove heavy metals from wastewater effluents.The effects of reaction parameters（sodium hydroxide,material ratio,temprature and contact time） were monitored to specify the best synthesis conditions.PUS was chemically characterized by means of infrared spectroscopy（FTIR） and ultraviolet-visible（UV-Vis）.The simultaneous chelation performance of PUS towards selected heavy metals ions,Ni2＋,Cu2＋,Pb2＋,Zn2＋,Cd2＋ was discussed,showing that Ni2＋,Cu2＋,Pb2＋,Zn2＋ could be better chelated.It is indicated that the synthesized PUS is a potential remediation material when used for the treatment of wastewater containing metal ions.

The research on the adsorption effect on metal ions by immobilized marine algae

The process of adsorption of Cu^2+ Cd^2+ by immobilized marine algae was investigated, it can be noted from the results that, the process for biosorption of heavy metals (copper, cadmium) by immobilized Laminaria japonica can be described by the Banerm model. According to the model, the adsorption rate constant calculated was 0.107 8 and 0.030 28 min^-1 for Cu^2+ and Cd^2+ respectively. The experimental biosorption equilibrium data for Cu^2+ and Cd^2+ were in good agreement with those calculated by the Langmuir model. The maximum uptake capacity calculated was 83.3 and 112.4 mg/g for Cu^2+ and Cd^2+ according to the Langmuir model, respectively. The appetency of Laminaria japonica to Cu^2+ was better than Cd^2+.

Enhancement of removal efficiency of heavy metal ions by polyaniline deposition on electrospun polyacrylonitrile membranes

This paper describes the preparation of a membrane of polyacrylonitrile(PAN)and its corresponding membrane coated with polyaniline(PANI)for the adsorption of heavy metal ions.Scanning electron microscopy micrographs revealed that all the membranes exhibited nanofibrous morphology.The prepared membranes were characterized by Fourier transform infrared spectroscopy(FTIR).The prepared membranes were used as an adsorbent for hazardous heavy metal ions Pb^(2+) and Cr_(2)O^(2-)_(7).The adsorption capacity and the removal efficiency of the membranes were examined as function of the initial adsorbate concentration and pH of the medium.Coated membranes with PANI showed better adsorption performance and their direct current(DC)conductivities were correlated to heavy metal ion concentrations.Adsorption isotherms were also performed,and the adsorption process was tested according to the Langmuir and Freundlich models.The regeneration and reuse of the prepared membranes to re-adsorb heavy metal ions were also investigated.The enhancement in adsorption performance and reusability of PANI-coated membranes in comparison with non-coated ones is fully discussed.The results show that the maximum adsorption capacities of lead and chromate ions on the PANI-coated membranes are 290.12 and 1202.53 mg/g,respectively.

Metal Ions Extraction with Glucose Derivatives as Chelating Reagents in Supercritical Carbon Dioxide

A series of glucose derivatives have been used as chelating reagents to extract metal ions in supercritical carbon dioxide. With perfluoro-l-octanesulfonic acid tetraethylammonium salt as additive, glucose derivatives were selective for Sr^2＋ and Pb^2＋ extraction in supercritical carbon dioxide.

Air-Stable Ultrabright Inverted Organic Light-Emitting Devices with Metal Ion-Chelated Polymer Injection Layer

Here,this work presents an air-stable ultrabright inverted organic lightemitting device(OLED)by using zinc ionchelated polyethylenimine(PEI)as electron injection layer.The zinc chelation is demonstrated to increase the conductivity of the PEI by three orders of magnitude and passivate the polar amine groups.With these physicochemical properties,the inverted OLED shows a record-high external quantum efficiency of 10.0% at a high brightness of 45,610 cd m^(-2) and can deliver a maximum brightness of 121,865 cd m^(-2).Besides,the inverted OLED is also demonstrated to possess an excellent air stability(humidity,35%)with a half-brightness operating time of 541 h@1000 cd m^(-2) without any protection nor encapsulation.

Hydroxylated graphene quantum dots as fluorescent probes for sensitive detection of metal ions

Highly sensitive methods are important for monitoring the concentration of metal ions in industrial wastewater.Here,we developed a new probe for the determination of metal ions by fluorescence quenching.The probe consists of hydroxylated graphene quantum dots(H-GQDs),prepared from GQDs by electrochemical method followed by surface hydroxylation.It is a non-reactive indicator with high sensitivity and detection limits of 0.01μM for Cu2+,0.005μM for Al3+,0.04μM for Fe3+,and 0.02μM for Cr3+.In addition,the low biotoxicity and excellent solubility of H-GQDs make them promising for application in wastewater metal ion detection.

Generation characteristics of a metal ion plasma jet in vacuum discharge

To improve the performance of a metal ion plasma jet in vacuum discharge, an anode-insulated cone-cylinder electrode with insulating sleeve is proposed in this paper. Discharge characteristics and generation characteristics of plasma of the electrode are investigated, effects of diameter of insulating sleeve, variety of cathode material and length of the insulating sleeve on characteristics of metal ion plasma jet are discussed. Results indicate that a directional and steady plasma jet is formed by using the novel electrode with insulating sleeve under high vacuum conditions. Moreover, the properties of metal ion plasma jet are improved by using the aluminum cathode and thin and long insulating sleeve. The study provides strong support for research of vacuum metal ion plasma thruster and ion implantation technology.

Selective preparation of light aromatic hydrocarbons from catalytic fast pyrolysis vapors of coal tar asphaltene over transition metal ion modified zeolites

The catalytic cracking of coal tar asphaltene(CTA)pyrolysis vapors was carried out over transition metalion modified zeolites to promote the generation of light aromatic hydrocarbons(L-ArHs)in a pyrolysisgas chromatography/mass spectrometry(Py-GC/MS)micro-reactor system.The effects of ultra stable Y(USY),Co/USY and Mo/USY on the selectivity and yield of L-ArHs products and the extent of deoxygenation(Edeoxygenation),lightweight(Elightweight)from CTA pyrolysis volatiles were investigated.Results showed that the yields of L-ArHs are mainly controlled by the acid sites and specific surface area of the catalysts,while the deoxygenation effect is determined by theirs pore size.The Eligltweight of CTA pyrolysis volatiles over USY is 9.65%,while the Edeoxygenation of CTA pyrolysis volatiles over Mo/USY reaches 20.85%.Additionally,the modified zeolites(Mo/USY and Co/USY)exhibit better performance than USY on L-ArHs production,owing to the synergistic effect of metal ions(Mo,Co)and acid sites of USY.Compared with the non-catalytic fast pyrolysis of CTA,the total yield of L-ArHs obtained over USY(4032 mg·kg^(-1)),Co/USY(4363 mg·kg^(-1))and Mo/USY(4953 mg·kg^(-1))were increased by 27.03%,38.19%and 54.78%,respectively.Furthermore,the possible catalytic conversion mechanism of transition metal ion(Co and Mo)modified zeolites was proposed based on the distribution of products and the characterizations of catalysts.

Sensitive Determination of DNA by RLS Enhancement of Metal Ions

The interactions between metal ions and DNA have been studied by the resonance light scattering (RLS) spectra. In the acidic condition, the RLS signals of metal ions, especially the transition metal ions in group IB and IIB, were increased by DNA. And it is found that the enhancement of RLS signals is linear to the concentration of DNA, so the RLS method for DNA determination was proposed in the presence of Cu2+. On the optimum conditions, the linear range and the detect limit of ctDNA is 4×10?8–4×10?6 g· mL?1 and 1. 13×10?8 g·mL?1, respectively. The proposed method is successfully applied to determine the extracted plasmid DNA ofBacillus subtilis DB104. Key words resonance light scattering - DNA - metal ions CLC number O 657.3 Foundation item: Supported by National Natural Science Foundation of China (20275028) and the National Key Basic Research and Development Program (973 Program 2002CB211800).Biography: Huang Jian-ping(1964-), male, Associate professor, research direction: bioanalysis.

Selective exchange of alkali metal ions on EAB zeolite

EAB zeolite was successfully prepared and applied to selective adsorption of Li^(+),Na^(+)and K^(+)ions.The physical and chemical properties of the adsorbent were characterized by X-ray diffraction(XRD),X-ray fluorescence(XRF),scanning electron microscope(SEM)and thermogravimetry(TG)methods.The ion exchange behaviours for Li^(+),Na^(+)and K^(+)ions in monomcomponent and multicomponent solutions were studied.In independent ion exchange,the ion exchange capacities ratiosα(/Na/Li)andα(K/Li)were 3.8 and 6.2,respectively.In competitive ion exchange,the selectivitiesβ(Na/Li)andβ(K/Li)increased with the initial concentrations and reached 409 and 992 when the initial concentrations was 100 mmol/L.The thermodynamic study results showed that Gibbs free energy change(ΔGΘ)of ion exchange reaction between Li-EAB and K^(+)was-34.96 kJ/mol,indicating that ion exchange of K^(+)ions was more energetically favourable than Li^(+)ions.The calculation results showed that the energy barriers of ion exchange increased in the order K^(+)Na^(+)<Li^(+).The study shows that EAB zeolite is potential to be used in the separation of alkali ions.

Synthesis of a novel calix[4]arene-based fluorescent ionophore and its metal ions recognition properties

A novel fluorescent ionophore derived from calix[4]arene and pyrazoline was designed and synthesized.Its molecular structure was confirmed by ^1H NMR and element analysis.The resulting material shows specific fluorescent behavior toward the Zn^2＋ion among the other divalent metal ions,such as Co^2＋,Ni^2＋,Cu^2＋.The primary results indicate this ionophore material is a potential material for developing efficient fluorescent Zn^2＋ chemosensors.

Electrochemical Sensing of Heavy Metal Ions based on Monodisperse Single-crystal Fe_3O_4 Microspheres

Single-crystal FeOwith monodisperse microspheres structure has been used for individual electrochemical detection of heavy metal ions. Morphology and structure of the as-prepared FeOmicrospheres were characterized by scanning electron microscopy(SEM), transmission electron microscopy(TEM) and X-ray diffraction(XRD). Meanwhile the electrochemical properties of the FeOmicrospheres modified glass carbon electrodes(GCE) were characterized by cyclic voltammetry(CV) and electrochemical impedance spectroscopy(EIS), and the enhanced electrochemical response in stripping voltammetry for individual detection of Pb(Ⅱ), Hg(Ⅱ), Cu(Ⅱ), and Cd(Ⅱ) was evaluated using square wave anodic stripping voltammetry(SWASV). With high specific surface area and excellent catalytic activity toward heavy metal ions, the as-prepared monodisperse and single-crystal FeOmicrospheres show a preferable sensing sensitivity(22.2 μA/μM) and limit of detection(0.0699 μM) toward Pb(Ⅱ). Furthermore, the electrochemical sensor of FeOmicrospheres exhibits excellent stability and it also offers potential practical applicability for the determination of heavy metal ions in real water samples. This study provides a potential simple and low cost iron oxide for the construction of sensitive electrochemical sensors applied to monitor and control the pollution of toxic metal ions.

Sorption Characteristics for Multiple Adsorption of Heavy Metal Ions Using Activated Carbon from Nigerian Bamboo

Sorption characteristics of multiple adsorption of six heavy metal ions often found in refinery waste waters using activated carbon from Nigerian bamboo was investigated. The bamboo was cut, washed and dried. It was carbonized between 350℃ - 500℃, and activated at 800℃ using nitric acid. Simultaneous batch adsorption of different heavy metal ions (Cd2+, Ni2+, Pb2+, Cr3+, Cu2+ and Zn2+) in same aqueous solution using activated carbon from Nigerian bamboo was carried out. The adsorption process had a better fit for the Freundlich, Temkin isotherm and Dubinin-Radushke-vich (DRK) isotherm models but could not fit well into Langmuir isotherm. Adsorption isotherms showed that there is competition among various metals for adsorption sites on Nigerian bamboo. The DRK model was used to determine the nature of the sorption process and was found to be physical and chemical, with sorption energy of metal ions ranging from (7 - 10 kJ/mol). The adsorption of Cd2+, Zn2+, Pb2+ and Ni2+ ions was chemisorptions and that of Cu2+ and Cr3+ ions was cooperative adsorption. Therefore, this study revealed that Nigerian bamboo can serve as a good source of activated carbon with multiple and simultaneous metalions—removing potentials and may serve as a better replacement for commercial activated carbons in applications that warrant their use.