Adsorption of Ce(Ⅳ) Anionic Nitrato Complexes onto Anion Exchangers and Its Application for Ce(Ⅳ) Separation from Rare Earths(Ⅲ)

Ce （Ⅳ） nitrato complexes were adsorbed on two anion exchangers based on polyvinyl pyridine （PVP） and quatemized PVP incorporated into porous silica matrix. The effect of nitric acid concentration （0.5～6 mol·L^-1） and temperature （278 ～318 K） on Ce（ Ⅳ ） sorption efficiency was investigated. Sorption increased with increasing nitric acid concentration, indicating that [Ce（NO3）6]^2- complex is the main adsorbed Ce（Ⅳ） species. Oxidation of sorbents by adsorbed Ce （ Ⅳ ） species resulting in Ce （ Ⅲ ） release to the solution was observed. Pyridine based anion exchangers exhibited higher oxidation stability compared to the commercial strong base anion exchanger. Ce（ Ⅳ ） reduction was temperature dependent and obeyed pseudo-first-order reaction kinetics. Column separation of Ce （ Ⅳ ） from La （ Ⅲ ） and Y （ Ⅲ ） was carried out from 6 mol·L^-1 nitric acid with PVP based anion exchanger. Reasonable Ce （Ⅳ） breakthrough capacity （0.7 mol·kg^-1 PVP） was achieved. No remarkable decrease of capacity was observed within 3 consequent runs. In contrast, Ce （Ⅲ） leakage due to reduction decreased and breakthrough capacity slightly increased. This effect was more pronounced with increasing temperature. Regeneration with 0.1 mol·L^- 1 nitric acid was successful （recovery 100% ± 4% ） and Ce solution of high purity （ 〉 99.97% ） with respect to La and Y content was gained.

Effects of Polar Organic Solvent on Separation of Y(edta)^-/Nd(edta)^- Complexes on Polyacrylic Anion Exchangers

The use of polar organic solvents for the separations of rare earth elements (Ⅲ) is effective especially for their extensive separations despite the solubility limitations. The study shows that polyacrylate anion exchangers, particularly the weakly basic, gel anion exchanger Amberlite IRA 68, can be applied to the separation of rare earth complexes with EDTA in H_2O-methanol and H_2O-ethanol systems. In most cases the determined distribution coefficients of Ln^(3+) complexes with EDTA in mixed media like water-methanol on polyacrylate anion exchangers are larger than those in pure water (media.)

Synthesis and Modulation of Low-Dimensional Transition Metal Chalcogenide Materials via Atomic Substitution

In recent years,low-dimensional transition metal chalcogenide(TMC)materials have garnered growing research attention due to their superior electronic,optical,and catalytic properties compared to their bulk counterparts.The controllable synthesis and manipulation of these materials are crucial for tailoring their properties and unlocking their full potential in various applications.In this context,the atomic substitution method has emerged as a favorable approach.It involves the replacement of specific atoms within TMC structures with other elements and possesses the capability to regulate the compositions finely,crystal structures,and inherent properties of the resulting materials.In this review,we present a comprehensive overview on various strategies of atomic substitution employed in the synthesis of zero-dimensional,one-dimensional and two-dimensional TMC materials.The effects of substituting elements,substitution ratios,and substitution positions on the structures and morphologies of resulting material are discussed.The enhanced electrocatalytic performance and photovoltaic properties of the obtained materials are also provided,emphasizing the role of atomic substitution in achieving these advancements.Finally,challenges and future prospects in the field of atomic substitution for fabricating low-dimensional TMC materials are summarized.

Influence of Al_(2)O_(3)/SiO_(2) Ratio on the Structure and Properties of Na^(+)/K^(+)Ion Exchange Na_(2)O-MgO-Al_(2)O_(3)-SiO_(2) Glasses

In this work,the structure,viscosity and ion-exchange process of Na_(2)O-MgO-Al_(2)O_(3)-SiO_(2) glasses with different Al_(2)O_(3)/SiO_(2) molar ratios were investigated.The results showed that,with increasing Al_(2)O_(3)/SiO_(2) ratio,the simple structural units Q_(1) and Q_(2) transformed into highly aggregated structural units Q_(3) and Q_(4),indicating the increase of polymerization degree of glass network.Meanwhile,the coefficient of thermal expansion decreased from 9.23×10^(-6)℃^(-1) to 8.88×10^(-6)℃^(-1).The characteristic temperatures such as melting,forming,softening and glass transition temperatures increased with the increase of Al_(2)O_(3)/SiO_(2) ratio,while the glasses working temperature range became narrow.The increasing Al_(2)O_(3)/SiO_(2) ratio and prolonging ion-exchange time enhanced the surface compressive stress(CS)and depth of stress layer(DOL).However,the increase of ion exchange temperature increased the DOL and decreased the CS affected by stress relaxation.There was a good linear relationship between stress relaxation and surface compressive stress.Chemical strengthening significantly improved the hardness of glasses,which reached the maximum value of(622.1±10)MPa for sample with Al_(2)O_(3)/SiO_(2) ratio of 0.27 after heat treated at 410℃for 2 h.

San copolymer membranes with ion exchangers for Cu(Ⅱ)removal from synthetic wastewater by electrodialysis

Heterogeneous membranes were obtained by using styrene-acrylonitrile copolymer（SAN）blends with low content of ion-exchanger particles（5 wt.%）. The membranes obtained by phase inversion were used for the removal of copper ions from synthetic wastewater solutions by electrodialytic separation. The electrodialysis was conducted in a three cell unit, without electrolyte recirculation. The process, under potentiostatic or galvanostatic control, was followed by p H and conductivity measurements in the solution. The electrodialytic performance,evaluated in terms of extraction removal degree（rd） of copper ions, was better under potentiostatic control then by the galvanostatic one and the highest（over 70%） was attained at8 V. The membrane efficiency at small ion-exchanger load was explained by the migration of resin particles toward the pores surface during the phase inversion. The prepared membranes were characterized by various techniques i.e. optical microscopy, Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis and differential thermal analysis and contact angle measurements.

Efficient conversion of CO_(2) into cyclic carbonates under atmospheric by halogen and metal-free poly(ionic liquid)s

A novel series of halogen free, hydroxyl group containing poly(ionic liquid)s(PILs) was first synthesized from glycerol dimethyl acrylate(GDA) and 1-vinyl imidazole(1-VIM) through free radical polymerization, follow by an alkylation step and an ion-exchange procedure to form the final imidazolium hydrogen carbonate heterogenous catalyst poly(HCO_(3)-OH-n). The chemical and physical properties were investigated by varying the monomer ratio between GDA and 1-VIM. Among them, poly(HCO_(3)-OH-2) exhibited the highest catalytic activity for CO_(2)cycloaddition, with the yield of chloropropene carbonate 90% under mild conditions(80℃, 0.1 MPa, 12 h, 0.15 g catalyst for 32 mmol epichlorohydrin) in the absence of any cocatalyst, metal or solvent. A range of substrates with good to excellent yields under atmosphere was obtained. The poly(HCO_(3)-OH-n) catalyst is collectable and still remains acceptable catalytic activity after six runs. Finally, a preliminary kinetic is calculated on the basis of poly(HCO_(3)-OH-2) with the activation energy value of 79.5 kJ·mol^(-1). This study highlights that the poly(HCO_(3)-OH-n) enable to reach efficient CO_(2) conversion under mild conditions.

Determination of Sc by Ion-exchanger Colorimetry

Ion exchanger colorimetry for scandium in the form of ternary color system “Sc(Ⅲ) CPA pc Ac” was developed. The influences of types and grain sizes of resin, adsorption modes and the acidity on the determination were studied systematically, and the optimum operating conditions and the allowable amounts of foreign ions were determined. In comparison with the ordinary solution colorimetry, both of the sensitivity and the selectivity of this ion exchanger colorimetry are improved obviously. The preliminary uses of this method to the determination of Sc(Ⅲ) in two synthetic samples were satisfied.

Defective layered Mn-based cathode materials with excellent performance via ion exchange for Li-ion batteries

Defective layered Mn-based materials were synthesized by Li/Na ion exchange to improve their electrochemical activity and Coulombic efficiency.The annealing temperature of the Na precursors was important to control the P3-P2 phase transition,which directly affected the structure and electrochemical characteristics of the final products obtained by ion exchange.The O3-Li_(0.78)[Li_(0.25)Fe_(0.075)Mn_(0.675)]O_(δ) cathode made from a P3-type precursor calcined at 700℃ was analyzed using X-ray photoelectron spectrometry and electron paramagnetic resonance.The results showed that the presence of abundant trivalent manganese and defects resulted in a discharge capacity of 230 mAh/g with an initial Coulombic efficiency of about 109%.Afterward,galvanostatic intermittent titration was performed to examine the Li^(+) ion diffusion coefficients,which affected the reversible capacity.First principles calculations suggested that the charge redistribution induced by oxygen vacancies(OV_(s))greatly affected the local Mn coordination environment and enhanced the structural activity.Moreover,the Li-deficient cathode was a perfect match for the pre-lithiation anode,providing a novel approach to improve the initial Coulombic efficiency and activity of Mn-based materials in the commercial application.

A potential-responsive ion-pump system based on nickel hexacyanoferrate film for selective extraction of cesium ions

A nickel hexacyanoferrate(NiHCF)film electrode was prepared with NiHCF,conductive carbon black,and polyvinylidene difluoride,which was coated on graphite plate substrate for selective extraction of Cs^(+)ions by using electrochemically switched ion exchange(ESIX)technology.A potential-responsive ionpump system for efficient extraction of Cs+ions was designed,and the effect of wet film thicknesses,charging modes,flow rates,and chamber widths on Cs+ions extraction performance was investigated.In the system,the adsorption capacity and removal percentage of Cs^(+)ions on the NiHCF film electrode reached as high as 147.69 mg·g^(-1)and 92.47%,respectively.Furthermore,the NiHCF film electrode showed high selectivity for Cs^(+)ions and stability.After seven cycles of adsorption/desorption,the desorption percentage could reach about 100%.The excellent Cs^(+)extraction performance should be attributed to the strong driving force produced by the potential-responsive ion-pumping effect in the ESIX process,as well as the low ion transfer resistance of the film electrode which is caused by the special crystal structure of NiHCF.In addition,the NiHCF film electrode was implemented to work together with the bismuth oxybromide(BiOBr)film electrode to accomplish the simultaneous extraction of Cs^(+)and Br^(-).And the adsorption capacity and removal percentage of Br^(-)ions on the BiOBr film electrode reached 69.53 mg·g^(-1)and 77.32%,correspondingly.It is expected that such a potential-responsive ion-pump system based on NiHCF and BiOBr film electrodes could be used for the selective extraction and concentration of Cs^(+)and Br^(-)ions from salt lake brine.

Advances and challenges of electrolyzers for large-scale CO_(2) electroreduction

CO_(2) electroreduction(CO_(2) ER)to high value-added chemicals is considered as a promising technology to achieve sustainable carbon neutralization.By virtue of the progressive research in recent years aiming at design and understanding of catalytic materials and electrolyte systems,the CO_(2) ER performance(such as current density,selectivity,stability,CO_(2) conversion,etc.)has been continually increased.Unfortunately,there has been relatively little attention paid to the large-scale CO 2 electrolyzers,which stand just as one obstacle,alongside series-parallel integration,challenging the practical application of this infant technology.In this review,the latest progress on the structures of low-temperature CO_(2) electrolyzers and scale-up studies was systematically overviewed.The influence of the CO_(2) electrolyzer configurations,such as the flow channel design,gas diffusion electrode(GDE)and ion exchange membrane(IEM),on the CO_(2) ER performance was further discussed.The review could provide inspiration for the design of large-scale CO_(2) electrolyzers so as to accelerate the industrial application of CO_(2) ER technology.

Biosorption of copper ions from dilute aqueous solutions on base treated rubber (Hevea brasiliensis) leaves powder: kinetics, isotherm, and biosorption mechanisms

The effciency of sodium hydroxide treated rubber (Hevea brasiliensis) leaves powder (NHBL) for removing copper ions from aqueous solutions has been investigated. The e?ects of physicochemical parameters on biosorption capacities such as stirring speed, pH, biosorbent dose, initial concentrations of copper, and ionic strength were studied. The biosorption capacities of NHBL increased with increase in pH, stirring speed and copper concentration but decreased with increase in biosorbent dose and ionic strength. The isotherm study indicated that NHBL fitted well with Langmuir model compared to Freundlich and Dubinin-Radushkevich models. The maximum biosorption capacity determined from Langmuir isotherm was 14.97 mg/g at 27°C. The kinetic study revealed that pseudo- second order model fitted well the kinetic data, while Boyd kinetic model indicated that film diffusion was the main rate determining step in biosorption process. Based on surface area analysis, NHBL has low surface area and categorized as macroporous. Fourier transform infrared (FT-IR) analyses revealed that hydroxyl, carboxyl, and amino are the main functional groups involved in the binding of copper ions. Complexation was one of the main mechanisms for the removal of copper ions as indicated by FT-IR spectra. Ion exchange was another possible mechanism since the ratio of adsorbed cations (Cu2+ and H+) to the released cations (Na+, Ca2+, and Mg2+) from NHBL was almost unity. Copper ions bound on NHBL were able to be desorbed at > 99% using 0.05 mol/L HCl, 0.01 mol/L HNO3, and 0.01 mol/L EDTA solutions.

Pb(Ⅱ) biosorption using chitosan and chitosan derivatives beads: Equilibrium, ion exchange and mechanism studies

The study examined the adsorption of Pb（II） ions from aqueous solution onto chitosan, chitosan-GLA and chitosan-alginate beads. Several important parameters influencing the adsorption of Pb（II） ions such as initial pH, adsorbent dosage and different initial concentration of Pb（II） ions were evaluated. The mechanism involved during the adsorption process was explored based on ion exchange study and using spectroscopic techniques. The adsorption capacities obtained based on non–linear Langmuir isotherm for chitosan, chitosan-GLA and chitosan-alginate beads in single metal system were 34.98, 14.24 and 60.27 mg/g, respectively. However, the adsorption capacity of Pb（II） ions were reduced in the binary metal system due to the competitive adsorption between Pb（II） and Cu（II） ions. Based on the ion exchange study, the release of Ca2＋, Mg2＋, K＋ and Na＋ ions played an important role in the adsorption of Pb（II） ions by all three adsorbents but only at lower concentrations of Pb（II） ions. Infrared spectra showed that the binding between Pb（II） ions and the adsorbents involved mostly the nitrogen and oxygen atoms. All three adsorbents showed satisfactory adsorption capacities and can be considered as an efficient adsorbent for the removal of Pb（II） ions from aqueous solutions.

A study of phosphate adsorption by different temperature treated hydrous cerium oxides

An alkaline precipitation method was introduced to produce hydrous cerium oxides.The prepared powder was characterized by Brunauer-Emmett-Teller（BET） nitrogen adsorption-desorption,X-ray diffraction（XRD）,Fourier transform infrared（FTIR） spectrometry,and thermal gravimetry（TG） approaches.The adsorbent has a chemical formula of CeO2·nH2O（n 2） and a cubic fluorite-type structure after high temperature treatment.Adsorption capacity of different temperature treated hydrous cerium oxides does not directly correlate with BET specific surface area.Phosphate adsorption isotherms follow the Langmuir equation below the treatment temperature of 800°C.Phosphate adsorption causes no change on the structure of a hydrous cerium oxides,and no signs of CePO4 precipitates are found.The ion-exchanging structure of hydrous cerium oxide plays a fundamental role in phosphate adsorption.The structure is highly temperature resistant and forms adsorption sites which adsorb both water and some anions.Complete loss of adsorption ability cannot be achieved unless the treatment temperature is higher than 1200°C.Mechanism study shows that the adsorption of phosphates is mainly an anion-exchange process.

KNaY-zeolite catalyzed dehydration of methyl lactate

A promising catalyst, KNaY was prepared by an ion exchange method with aqueous potassium chloride solution, Compared with NaY, KNaY was an effective catalyst for the dehydration of methyl lactate to methyl acrylate. Under the optimized conditions, an improved yield of 37.9 mol% was achieved.

Synthesis, structure characterization, and ion exchange properties of a novel open-framework ecomaterial silicotitanate

A novel open-framework ecomaterial silicotitanate (Na_4Ti_4Si_3O_(10)) wassynthesized by a combination of solgel and hydrothermal methods. The investigation on ion exchangeproperties shows that Na_4Ti_4Si_3O_(10) exhibits high ad-sorption for cesium, i.e., K_d is as highas 60 000 mL/g in neutral solution. The crystal structure of Na_4Ti_4Si_3O_(10) was characterized byX-ray difiraction (XRD), scanning electronic microscope (SEM), transmission electron microscope(TEM), Raman spectrum, differential thermal and thermogravimetric analysis (DTA/TGA), inductivelycoupled plasma (ICP), and X fluorescence analysis. The compound is tetragonal, P4_2, a=b = 0.781 10nm, c = 1.196 45 nm, alpha =beta = gamma = 90 deg, Z = 4, and R^a = 0.041; Na_4Ti_4Si_3O_(10) has athree dimensional framework consisting of Ti-O octahedral clusters and Si-O tetrahedra. The resultsshow that Na_4Ti_4Si_3O_(10) has good chemical stability, thermal stability, and high cesium ionexchange capacity in the whole pH range.

Adsorption equilibrium and kinetics studies of divalent manganese from phosphoric acid solution by using cationic exchange resin

There are numerous impurities in wet-process phosphoric acid,among which manganese is one of detrimental metallic impurities,and it causes striking negative effects on the industrial phosphoric acid production and downstream commodity.This article investigated the adsorption behavior of manganese from phosphoric acid employing Sinco-430 cationic ion-exchange resin.Resorting FT-IR and XPS characterizations,the adsorption mechanism was proved to be that manganese was combined with sulfonic acid group.Several crucial parameters such as temperature,phosphoric acid content and resin dose were studied to optimize adsorption efficiency.Through optimization,removal percentage and sorption capacity of manganese reached 53.12 wt%,28.34 mg·g^-1,respectively.Pseudo-2nd-order kinetic model simulated kinetics data best and the activation energy was evaluated as 6.34 kJ·mol^-1 for the sorption reaction of manganese.In addition,the global adsorption rate was first controlled by film diffusion process and second determined by pore diffusion process.It was found that the resin could adsorb up to 50.24 mg·g^-1 for manganese.Equilibrium studies showed that Toth adsorption isotherm model fitted best,followed by Temkin and Langmuir adsorption isotherm models.Thermodynamic analysis showed that manganese adsorption was an endothermic process with enhanced randomness and spontaneity.

A novel protein refolding method integrating ion exchange chromatography with artificial molecular chaperone

Artificial molecular chaperone （AMC） and ion exchange chromatography （IEC） were integrated, thus a new refolding method, artificial molecular chaperone-ion exchange chromatography （AMC-IEC） was developed. Compared with AMC and IEC, the activity recovery of lysozyme obtained by AMC-IEC was much higher in the investigated range of initial protein concentrations, and the results show that AMC-IEC is very efficient for protein refolding at high concentrations. When the initial concentration of lysozyme is 180 mg/mL, its activity recovery obtained by AMC-IEC is still as high as 76.6%, while the activity recoveries obtained by AMC and IEC are 45.6% and 42.4%, respectively.

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.

Revealing the critical effect of solid electrolyte interphase on the deposition and detriment of Co(Ⅱ) ions to graphite anode

"Dissolution,migration,and deposition"of transition metal ions (TMIs) result in capacity degradation of lithium-ion batteries (LIBs).Understanding such detrimental mechanism of TMIs is critical to the development of LIBs with long cycle life.In most previous works,TMIs were directly introduced into the electrolyte to investigate such a detrimental mechanism.In these cases,the TMIs are deposited directly on the fresh anode surface.However,in the practical battery system,the TMIs are deposited on the anode covered with solid electrolyte interphase (SEI) film.Whether the pre-presence of SEI film on anode surface influences the deposition and detriment of TMIs is unclear.In this work,the deposition of Co element on graphite anode with and without SEI film were systematically studied.The results clearly show that,in comparison with that of fresh graphite (SEI-free),the presence of SEI film aggravates the deposition of Co ions due to the Li^(+)–Co^(2+) ion exchange between the SEI and Co^(2+)-containing electrolyte without the driving of the electric field,leading to faster capacity fading of graphite anode.Therefore,how to regulate electrolytes and film-forming additives to design the components of SEI and prevent its exchange with TMIs,is a crucial way to inhibit the deposition and detriment of TMIs on graphite anode.

Mineral sulphide-lime reactions and effect of CaO/C mole ratio during carbothermic reduction of complex mineral sulphides

Mineral sulphide （MS）-lime （CaO） ion exchange reactions （MS ＋ CaO = MO ＋ CaS） and the effect of CaO/C mole ratio during carbothermic reduction （MS ＋ CaO ＋ C = M ＋ CaS ＋ CO（g）） were investigated for complex froth flotation mineral sulphide concentrates. Phases in the partially and fully reacted samples were characterised by X-ray diffraction （XRD） and scanning electron microscopy （SEM）. The primary phases during mineral sulphide-lime ion exchange reactions are Fe304, CaSO4 Cu2S, and CaS. A complex liquid phase of Ca2CuFeO3S forms during mineral sulphide-lime exchange reactions above 1173 K. The formation mechanisms of Ca2CuFeO3S liquid phase are determined by characterising the partially reacted samples. The reduction rate and extent of mineral sulphides in the presence of CaO and C increase with the increase in CaO/C ratio. The metallic phases are surrounded by the CaS rich phase at CaO/C 〉 1, but the metallic phases and CaS are found as separate phases at CaO/C 〈 1. Experimental results show that the stoichiometric ratio of carbon should be slightly higher than that of CaO. The reactions between CaO and gangue minerals （SiO2 and A1203） are only observed at CaO/C 〉 1 and the reacted samples are excessively sintered.