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.

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.

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.

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.

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.

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.

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.

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.

Comparative adsorption of heavy metal ions in wastewater on monolayer molybdenum disulfide

To maximize the potential of monolayer molybdenum disulfide(MoS2)sheet in the disposal of heavy metal ions in wastewater,we compared the adsorption of several common heavy metal ions(including Cr^(3+),Ni^(2+),Cu^(2+),Zn^(2+),Cd^(2+),Hg^(2+),and Pb^(2+))in wastewater on the monolayer MoS2 sheet through first-principles calculation.Our simulation results show that the monolayer MoS2 sheet is a potential heavy metal adsorption material because of the attractive interaction between them.The most negative adsorption energy determines that the TMo site is the most stable adsorption site for the heavy metal ions.The attractive interaction is considered as chemical adsorption,and it is closely related to charge transfer.The orbital hybridization between S p and heavy metal ions p and d states electrons contributes to the adsorption,except the orbital hybridization between S p and Pb p states electrons contributes to the Pb^(2+) adsorption.All the results show that the monolayer MoS2 sheet is most suitable for removing Ni^(2+) and Cr^(3+) ions from wastewater,followed by Cu^(2+) and Pb^(2+).For the ions Cd^(2+),Zn^(2+),and Hg^(2+),its adsorption strength remains to be improved.

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.

Solid-liquid solvent extraction of metal ions

An overview of extraction of some trace metal ions using molten solvent (lowmelting substance) during last two decades is presented. The development of this technique since itsinception is briefly traced. The comparison of extraction efficiency, thermodynamics and kineticsmainly involving extraction of rare earth ions between molten solvent extraction at high temperatureand usual liquid-liquid extraction at room temperature are discussed in detail. The variousparameters obtained from the previous and present studies such as equilibrium extraction constantK_(ex), pH_(1/2), thermodynamic and kinetic data are displayed in tabular form. Finally, the currentdemands, disadvantages and future prospects are also evaluated.

Sensitive Determination of Metal Ions in Drinking Water by Capillary Electrophoresis Coupled with Contactless Conductivity Detection Using 18-Crown-6 Ether and Hexadecyltrimethylammonium Bromide as Complexing Reagents

A simple, economical, and sensitive capillary electrophoresis (CE) method integrated with capacitively coupled contactless conductivity detection was developed for the determination of metal ions such as K+, Na+, Mg2+, Sr2+, Ca2+ in drinking water. 18-Crown-6 ether and Hexadecyltrimethylammonium Bromide (CTAB) were employed as complexing reagents. The effects of electrolyte additives, citric acid buffer solution, and other separation conditions of CE were comprehensively investigated and carefully optimized. The best results were obtained in a running buffer solution composed of citric acid (12 mM), 18-crown-6 ether (0.2 mM), and CTAB (0.015 mM) at pH 3.5. Under these conditions, a complete separation of five metal ions was successfully achieved in less than 12 min. The limits of detection for the optimal procedure were determined to be in the range of 0.02 - 0.2 mg·L-1. The repeatability with respect to migration times and peak areas, expressed as relative standard deviations, was better than 2.3% and 5.1%, respectively. Evaluation of the efficiency of the methodology indicated that it was reliable for the determination of metal ions in six different brands of drinking water samples.

Chelation Assignments of Ga^Ⅲ,Ge^Ⅳand Si^ⅣMetal Ions WithPipemidic Acid Antibiotic Drug:Synthesis,Spectroscopic Characterizations and Biological Studies

Pipemidic acid is one of an efficient quinolone antibacterial drug.Thecomplexitybetween pipemidic acid“Hpipc”withgallium(Ⅲ),germanium(Ⅳ)and silicon(Ⅳ)afforded three molecular formulas of[Ga(pipc)2(H 2O)(Cl)]·4H 2O,1,[Ge(pipc)2(Cl)2]·4H 2O,2 and[Si(pipc)2(Cl)2]·4H 2O,3 complexes.These three new complexes were characterized based on elemental analysis,conductance,FTIR,UV-Vis,^1HNMR and XRD spectroscopy.The pipc chelate exhibits O,O coordinated through the carbonyl(C O)and carboxylato(COO)of both oxygen atoms.Six coordinate geometry was proposed regarding complexes of 2 and 3,so the axial position was occupied by two coordinated chlorideatoms.In vitro,the antibacterial,antifungal,and anti-cancer assessments concerning the synthesized pipc complexes were scanned.These complexes have an excellent anti-microbial activity.

A Highly Sensitive Kinetic Spectrophotometric System and Its Analytical Potential for Chromatographic Detection of Metal Ions

Based on the inhibitory effect of metal ions on the decolourization reaction of a dye taking place in a mixed micellar medium, a differential rate method was developed for the detection of metal ions. The present kinetic spectrophotometric system has several advantages due to introduction of the mixed micelles.

Study on a New Method of Extraction of Metal Ions from SolidMatrices by Supercritical Fluid

8-Hydroxyquinoline, methanol and Triton-100 were first used together in the extraction of metal ions by supercritical CO2. In the new system, the effects of pressure, temperature and the volume of CO2 on the efficiency of supercritical fluid extraction (SFE) were systematically investigated. The recovery under the optimum condition was only 11.38%, but if suitable concentration of methanol (v/v=5%) was added to the supercritical CO2, the recovery was increased significantly (83.60%, RSD=4.37%, n=5). In order to further enhance the recovery Triton X-100 was added to the samples, and the results were satisfactory (96.62%, RSD=2.85%, n=5).

Effect of alkali metal ions on the formation mechanism of HCN during pyridine pyrolysis

The catalytic effects of alkali metal ions(Na^(+)and K^(+))on NO_(x)precursor formation during coal pyrolysis were investigated using the N-containing compound pyridine as a model compound.Density functional theory calculations at the B3LYP/6-31G(d,p)level of theory were conducted to elucidate the mechanism of pyridine pyrolysis and the pathways for HCN formation.The calculation results indicate that Na^(+)and K^(+)have distinct influences on different pyrolysis reactions;these alkali metal ions facilitate the initial hydrogen transfer from C_(1)to N and C_(2),whereas they hinder the other hydrogen migration reactions.Both Na^(+)and K^(+)significantly reduce the activation energies for C–C bond breakage and triple-bond formation,whereas they increase the activation energies for the isomerization reactions.The different effects essentially result from the distinct charge distributions induced by the two ions.Due to the distinct influences on the different reactions,the rate-determining steps are modulated,affecting the competitiveness of the different possible pathways of HCN formation.The formation of HCN from pyridine is promoted in the presence of Na^(+)and K^(+)because all the overall activation energies are decreased for different pathways.The calculation results agree well with previous experimental studies.Thus,the findings offer a new and promising approach to reveal the formation mechanism of NO_(x)and facilitate the control of NO_(x)for coal utilization.

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.