Simple, Selective, and Sensitive Spectrophotometric Method for Determination of Trace Amounts of Nickel(Ⅱ), Copper (Ⅱ), Cobalt (Ⅱ), and Iron (Ⅲ) with a Novel Reagent 2-Pyridine Carboxaldehyde Isonicotinyl Hydrazone

A selective and sensitive reagent of 2-pyridine carboxaldehyde isonicotinyl hydrazone（2-PYAINH） was synthesized and studied for the spectrophotometric determination of nickel, copper, cobalt, and iron in detail. At a pH value of 7.0, 9,0, 9.0, and 8.0, respectively, which greatly increased the selectivity; nickel, copper, cobalt, and iron reacted with 2-PYAINH to form a 1：2 yellow-orange, 1：2 yellow-green, 1：2 yellow and 1：1 yellow complexes, with absorption peaks at 363, 352, 346, and 359 nm, respectively. Under the optimal conditions, Beer＇s law was obeyed over the ranges of 0.01-1.4, 0.01-1.5, 0.01-2.7, and 0.01-5.4 mg/L respectively. The apparent molar absorptivity and Sandell＇s sensitivities were 8.4×10^4, 5.2×10^4, 7.1×10^4, and 3.9×10^4 L·mol^-l·cm^-1, respectively, and 0.00069, 0.0012, 0.00078, and 0.0014 μg·cm2, respectively. The detection limits were found to be 0.001, 0.002, 0.003, and 0.01 mg/L, respectively. The detailed study of various interfering ions to make the method more sensitive was carried out and selective and several real samples were analyzed with satisfactory results.

Effect of cerium ion(Ⅲ) on corrosion resistance of organic-inorganic hybrid coating on surface of aluminum-tube used in refrigeration equipment

Organic?inorganic hybrid coating on the surface of aluminum-tube used in refrigeration equipment using cerium ion (III) as the additive was fabricated by sol?gel method, and the structure of the coating was confirmed by FT-IR. The results of the characterization show that the corrosion resistance of the coating with 1.5 mmol/L cerium ion (III) gains significant improvement, in which the colour retention time of CuSO4 extends to 500 s, the anti-acid and alkali corrosion rates reduce by 67% and 70% compared with the blank one, respectively, and the salt spray tests also show good corrosion resistance. The electrochemical tests demonstrate that the self-corrosion current density and potential of the sample with hybrid coating are about 2.877×10?7 A/cm2 and?0.550 V, respectively. The metallographic and SEM images show that the hybrid coating is uniform and dense, and the EDS analysis confirms that the coating is mainly composed of Al, Si and Ce elements.

Adsorption behavior and mechanism of Bi(Ⅲ) ions on rutile-water interface in the presence of nonyl hydroxamic acid

The adsorption behavior and mechanism of Bi（Ⅲ） ions on the rutile-water interface were investigated through micro-flotation, Zeta potential measurement, adsorption amount measurement and X-ray photoelectron spectroscopy（XPS）. According to the results of micro-flotation, Bi（Ⅲ） ions could largely improve the rutile flotation recovery（from 62% to 91%）, and they could increase the activating sites and reduce the competitive adsorption between nonyl hydroxamic acid negative ions and OH-ions, which determined that Bi（Ⅲ） ions were capable of activating rutile flotation. The adsorption of Bi（Ⅲ） ions onto the rutile surface led to the shift of Zeta potential into the positive direction, which was good for the adsorption of nonyl hydroxamic acid anions. In addition, the results of XPS indicated that the chemical environment around Ti atom had not changed before and after the adsorption of Bi（Ⅲ） ions. Based on the adsorption mechanism of Bi（Ⅲ） ions, it was deduced that firstly Bi（Ⅲ） ions occupied the vacancies of the original Ca^2＋, Mg^2＋ and Fe^2＋ ions on the rutile surface; secondly Bi（Ⅲ） ions covered on the rutile surface in the form of hydroxides.

Effect of Fe(Ⅲ) on the bromate reduction by humic substances in aqueous solution

Humic substances are ubiquitous redox-active organic compounds of environment. In this study, experiments were conducted to determine the reduction capacity of humic acid in the man-ix of bromate and Fe（Ⅲ） solutions and the role of Fe（Ⅲ） in this redox process. The results showed that the humic acid regenerated Fe（Ⅱ） and reduced bromate abiotically. The addition of Fe（Ⅲ） could accelerate the bromate reduction rate by forming humic acid-Fe（Ⅲ） complexes. Iron species acts as electron mediator and catalyst for the bromate reduction by humic acid, in which humic acid transfers electrons to the complexed Fe（Ⅲ） to form Fe（Ⅱ）, and the regenerated Fe（Ⅱ） donate the electrons to bromate. The kinetics study on bromate reduction further indicated that bromate reduction by humic acid-Fe（Ⅲ） complexes is pH dependent. The rate decreased by 2-fold with the increase in solution pH by one unit. The reduction capacity of Aldrich humic acid was observed to be lower than that of humic acid or natural organic matter of Suwanne River, indicating that such redox process is expected to occur in the environment.

Adsorption behavior of Sb(Ⅲ) in single and binary Sb(Ⅲ)-Fe(Ⅱ) systems on cationic ion exchange resin: Adsorption equilibrium, kinetic and thermodynamic aspects

The present study dealt with the mechanism of competitive adsorption of Sb(Ⅲ)and Fe(Ⅱ)ions from a copper-containing aqueous solution on Purolite S957,a commercially available cationic ion-exchange adsorbent.Experiments were conducted using aqueous copper sulfate solutions containing either single or conjoint ions,using both sedentary and batch adsorption techniques to ascertain the sensitivity of the adsorption process to variation in p H,mass of resin,contact time,and temperature as well as establishing the optimal range of variables for maximum ion removal.The data from single ion adsorption tests were fitted by non-linear regression techniques to Henry,Langmuir,Freundlich,Temkin,and Dubinin–Radushkevich isotherm models.Freundlich isotherm for Sb(Ⅲ)and Freundlich and Henry models for Fe(Ⅱ)solutions best express the adsorption equilibrium data;while for binary ion electrolytes,the extended Freundlich model fitted the data satisfactorily.The kinetic model adequately describing adsorption was shown to be the pseudo-first-order,underscoring the dominant role of physical adsorption playing in the process.Thermodynamic parameters for the adsorption process reveal differences in the Sb(Ⅲ)adsorption mechanism from single ion and Sb(Ⅲ)-Fe(Ⅱ)containing electrolytes.The adsorption of Sb(Ⅲ)alone is endothermic,whereas the process becomes exothermic in the Sb(Ⅲ)-Fe(Ⅱ)system.

Kinetics and Mechanism of Iridium(Ⅲ)-Catalyzed Oxidation of Ethanol Amine by Cerium(Ⅳ) in Sulfuric Acid Media

In this study, the kinetics and mechanism of the iridium（ Ⅲ ） -catalyzed oxidation of ethanol amine（EAN） by cerium（Ⅳ） in a sulfuric acid medium was investigated using titrimetric technique of redox in a temperature range of 298--313 K. It was found that the reaction is of first order with respect to Ce（ Ⅳ ） and It（ Ⅲ ）, and a positive fractional order with respect to EAN. It was also found that the pseudo-first-order （ [EAN ] 〉〉 [ Ce （ Ⅳ） ] ） rate constant koba decreases with the increase of [ H^＋ ] and [ HSO^-4 ]. Under the protection of nitrogen gas, the reaction system can initiate the polymerization of acrylonitrile, indicating the generation of free radicals. On the basis of the experimental results, a suitable mechanism was proposed. From the dependence of koba on the concentration of hydrogen sulfate, Ce（SO4）2 was found to be the kinetically active species. The rate constants of the rote-determining step together with the activation parameters were evaluated.

Cr(Ⅲ)离子印迹聚合物的制备及性能研究

以Cr(Ⅲ)为模板离子,采用表面印迹法,将氨基化多壁碳纳米管改性为乙烯化多壁碳纳米管作为固体基质,通过印迹体系的优化,制备了一系列Cr(Ⅲ)离子印迹聚合物[Cr(Ⅲ)-IIPs]及相应的非印迹聚合物[Cr(Ⅲ)-NIPs].在较优实验条件下制备的Cr(Ⅲ)-IIP1,吸附量为3.82 mmol·g^(−1),印迹因子为1.65.通过扫描电子显微镜(SEM)、氮气吸附/脱附(BET)、红外光谱(FIR)、热重分析(TG)等对Cr(Ⅲ)-IIP1及相应的Cr(Ⅲ)-NIP1,进行结构表征和性能评价.研究结果表明,Cr(Ⅲ)-IIP1属于热稳定性良好的吸附材料,吸附行为符合准二级动力学模型和Freundlich等温吸附模型,以化学吸附和多分子层吸附为主;在“竞争离子”Co(Ⅱ)、Ni(Ⅱ)和Pb(Ⅱ)共存条件下,对Cr(Ⅲ)离子具有较强的吸附能力和良好的选择性.说明在较优实验条件下制备的Cr(Ⅲ)-IIP1,有望作为一种新型的Cr(Ⅲ)离子吸附材料,去除和回收废水中的Cr(Ⅲ)离子.

Deep removal of copper from cobalt sulfate electrolyte by ion-exchange

SP-C was applied for the removal of Cu^2＋ from simulated cobalt sulfate electrolyte containing Co2＋ 50 g/L and Cu2＋ 0.5-2.0 g/L. Experimental conditions included pH of 2-4, temperature of 20-60℃ and contact time of 10-40 min. The investigation demonstrated that SP-C had recommendable efficiency in adsorbing Cu2＋ from the electrolyte with 25- to 100-fold of Co2＋ The optimal adsorption conditions of SP-C were pH of 4, contact time of 30 min and ambient temperature. The study also showed that the loaded resin could be effectively eluted with 2.0 mol/L H2SO4 solution at a contact time of 40 min; the peak concentration of Cu2＋ in the eluate was about 35 g/L. The sorption characteristics of Cu2＋ by SP-C could be described by Langrnuir isotherm and the pseudo second-order kinetic equation. Infrared spectra showed that nitrogen atoms in the functional group coordinated with Cu2＋ to form coordination bands.

Cobalt Sulfide Confined in N-Doped Porous Branched Carbon Nanotubes for Lithium-Ion Batteries

Lithium-ion batteries(LIBs) are considered new generation of large-scale energy-storage devices.However,LIBs suffer from a lack of desirable anode materials with excellent specific capacity and cycling stability.In this work,we design a novel hierarchical structure constructed by encapsulating cobalt sulfide nanowires within nitrogen-doped porous branched carbon nanotubes(NBNTs)for LIBs.The unique hierarchical Co9S8@NBNT electrode displayed a reversible specific capacity of 1310 mAhg-1 at a current density of 0.1 Ag-1,and was able to maintain a stable reversible discharge capacity of 1109 mAhg-1 at a current density of 0.5 Ag-1 with coulombic efficiency reaching almost 100% for 200 cycles.The excellent rate and cycling capabilities can be ascribed to the hierarchical porosity of the one-dimensional Co9S8@NBNT internetworks,the incorporation of nitrogen doping,and the carbon nanotube confinement of the active cobalt sulfide nanowires offering a proximate electron pathway for the isolated nanoparticles and shielding of the cobalt sulfide nanowires from pulverization over long cycling periods.

Effect of fluoride addition on electrochemical behaviors of V(Ⅲ) in molten LiCl-KCl

X-ray photoelectron spectroscopy(XPS)and Raman spectroscopy were used to analyze the complexes in LiCl−KCl eutectic salt containing VCl_(3) and KF.The additional fluoride ions would replace chloride ions and combine with V(Ⅲ)to form VF_(6)^(3-).The electrochemical behavior of V(Ⅲ)was evaluated under condition of the molar concentration ratio of F−to Vn+(α)equal to 0:1,1:1,2:1,5:1,20:1 and 50:1,respectively.The results showed that a new reduction step appeared:VF_(6)^(3-)→V^(2+),and the reduction mechanism of vanadium ions became more complicated.The metallic vanadium was deposited on the tungsten electrode at−2.90 V in the LiCl−KCl melts for 6 h,and the products were characterized by SEM−EDS.It was indicated that the particle size of the product decreased with adding fluoride ions for the forming of the coordination compound VF_(6)^(3-).

聚合物改性膨润土对钢渣渗滤液及其Cr(Ⅲ)离子的阻隔与吸附特性研究

【目的】针对传统膨润土防渗衬垫在侵蚀性环境中防渗性能会大幅劣化的难题,自主研发了一种聚合物改性膨润土。【方法】通过渗透实验研究了聚合物改性膨润土对高盐溶液、强碱溶液和实际钢渣渗滤液的渗透系数,并采用Batch吸附实验探究了吸附时间、溶液pH值和溶液浓度对聚合物改性膨润土吸附钢渣渗滤液中Cr(Ⅲ)离子的影响。【结果】实验结果表明:未改性的钠化钙基膨润土对侵蚀性溶液的刚性壁渗透系数高达1×10^(-8)m/s,而聚合物改性膨润土对高盐、强碱和钢渣渗滤液的柔性壁渗透系数均小于1×10^(-11)m/s,且刚性壁渗透系数约为3×10^(-11)m/s,在高盐、强碱等侵蚀性环境中表现出更优越的防渗性能。【结论】聚合物改性膨润土对Cr(Ⅲ)的吸附量随着吸附时间、溶液pH值和溶液浓度的增加而增加。钠化钙基膨润土和聚合物改性膨润土对Cr(Ⅲ)吸附符合准二阶吸附动力学模型;Langmuir等温吸附模型更好地描述了钠化钙基膨润土和聚合物改性膨润土对Cr(Ⅲ)的吸附特性。

Fabrication and adsorption property of novel adsorbent for potential application to wastewater with Fe(Ⅲ) ions

The spherical macroporous cellulose(SMC) was fabricated using medical absorbent cotton as raw material and nano CaCO3 as porogenic agents.And then,the phenylglycine was grafted onto the SMC to obtain the novel spherical macroporous cellulose derivative adsorbent(PSMC).FT-IR and scanning electron microscope(SEM) were employed to characterize the adsorbents and Fe3+ ions served as model solute to evaluate the adsorption property of the adsorbents.The experimental results show that the amount of porogenic agents and the value of pH have obvious influence on adsorption capacity of the adsorbents.The data of adsorption kinetic and isotherm display that the adsorbents possess excellent equilibrium adsorption capacity(348.94 mg/g) and have a bright prospect and considerable potential in the treatment of Fe3+ ions in wastewater.

Electrochemical properties of some cobalt antimonides as anode materi-als for lithium- ion batteries

Some cobalt antimonides have been prepared and studied as the candidate anodematerials for lithium ion batteries. Reversible capacities of 424,423 and 546 mA.h.g^(-1) weremeasured at the first cycle for as-solidified CoSb_2, CoSb_3 and annealed CoSb_3 respectively. A lowlithium ions diffusion coefficient in the order of 10^(16) m^2.s^(-1) was estimated from thecoulometric titration measurements in the annealed CoSb_3 electrode. It was found that theelectrochemical properties of fine powders are significantly better than coarse powders. However theSEM picture shows that the nano-sized CoSb_3 powders gathered to larger granules, which worsenssomewhat the capacity retention of the nano-sized materials, although the volume capacities of theannealed and ball milled CoSb_3 remain near twice of that of graphite after 50 cycles.

Stabilising Cobalt Sulphide Nanocapsules with Nitrogen-Doped Carbon for High-Performance Sodium-Ion Storage

Conversion-type anode materials with a high charge storage capability generally su er from large volume expansion, poor electron conductivity, and sluggish metal ion transport kinetics. The electrode material described in this paper, namely cobalt sulphide nanoparticles encapsulated in carbon cages(Co9S8@NC), can circumvent these problems. This electrode material exhibited a reversible sodium-ion storage capacity of 705 mAh g^-1 at 100 mA g^-1 with an extraordinary rate capability and good cycling stability. Mechanistic study using the in situ transmission electron microscope technique revealed that the volumetric expansion of the Co9S8 nanoparticles is bu ered by the carbon cages, enabling a stable electrode–electrolyte interface. In addition, the carbon shell with high-content doped nitrogen significantly enhances the electron conductivity of the Co9S8@NC electrode material and provides doping-induced active sites to accommodate sodium ions. By integrating the Co9S8@NC as negative electrode with a cellulose-derived porous hard carbon/graphene oxide composite as positive electrode and 1 M NaPF6 in diglyme as the electrolyte, the sodium-ion capacitor full cell can achieve energy densities of 101.4 and 45.8 Wh kg^-1 at power densities of 200 and 10,000 W kg^-1, respectively.

Synthesis and Crystal Structure of trans(N)-(1,10-Phenanthroline)-bis (DL-Al aninato)-Cobalt( Ⅲ ) Chloridetrihydrate

The title compound was synthesized by the reaction of cis-[Co(phen)2Cl2]Cl·3H2O with DL-alanine at pH = 8, and isolated using a column chromatographic method. Its crystal structure was determined. The crystal structure belongs to mono-clinic system, space group P21/c, with a = 0. 9549(6) nm, b=2.3746(8) nm, c= 1.0782(4) nm, β=114.13(3)°? Z = 4, Dc= 1. 50 g/cm3. The final refinement converged to R = 0. 047 for 3246 independent observed reflections. In the octahedral coordination sphere formed by the cobalt atom and the coordinate atoms, N, O of DL-alan-inato ligands are in the configuration of trans-N ,N form.

Separation of indium(Ⅲ), gallium(Ⅲ), and zinc(Ⅱ) with Levextrel resin containing di(2-ethylhexyl) phosphoric acid (CL-P204): Part Ⅱ. Mechanism and kinetics of adsorbing indium(Ⅲ)

The mechanism of adsorbing indium(Ⅲ) from sulfate solutions with CL-P204Levextrel resin containing di(-2-ethylhexyl) phosphoric acid was examined by batch operation andinfrared spectra. The results showed that the P204 adsorbed on the resin behaved in the similar wayto solvent extraction except that it was as a monomer in resin adsorbing but in dimeric form insolvent extraction. Three factors including temperature, indium(Ⅲ) concentration of solution, andthe size of resin particles which influence the In^(3+)/H^+ exchange on CL-P204 Levextrel resin wereinvestigated by the modified limited batch technique in order to determine the kinetics ofIn^(3+)/H^+ exchange. It was found that the rate of ion exchange increased with the temperature andthe concentration of solution increasing and with the size of the resin particles decreasing.According to the expression developed by Boyd et al., the controlling factor of In^(3+)/H^+ exchangeon CL-P204 Levextrel resin was the diffusion through the resin particles. The effective diffusioncoefficient, activation energy, and entropy of activation in the particle-diffusion were determinedas 1.57 x 10^(-10) m^2/s, 11.9 kJ/mol, -84.1 J/(mol·K), respectively.

Electroreduction of Co(Ⅱ) and La(Ⅲ)in UreaMelt

Electroreduction of Co(Ⅱ)to metallic cohalt in urea melt is irrevsible in one step.The transfer coeffi-cient of electrode reaction of Co(Ⅱ)+2e=Co(O)and the diffusion coefficient of Co(Ⅱ)were determined.The lanthanum can be inductively codeposited with cobalt. The contents of lanthanum in cobalt-lanthanum de-posts increase with the shift of electrode potential to the negative direction and the raise of La(Ⅲ)/Co(Ⅱ)mo-lar ratio in the melt. The cyclic voltammetry,open circuit potential-time curve after potentiostatic electrolysisand electron probe analyas were used.

Adsorption of Rare Earth Ion La(Ⅲ) on Yunnan Bowl Tea Surface from Aqueous Solution

The adsorption characteristics of rare earth ion La(Ⅲ) on Yunnan bowl tea surface from aqueous solution and effects of various surfactants on the adsorption were studied. It was found that Yunnan bowl tea can adsorb strongly La(Ⅲ) and pH may affect drastically the adsorption amount of La(Ⅲ). The adsorption law of La(Ⅲ) on Yunnan bowl tea surface follows the Langmuir equation. The maximum adsorption amount of La(Ⅲ) can reach 15 mg·g (-1). A comprehensive adsorption model is suggested according to the experimental results.

Electrodeposited Cobalt-Iron Alloy Thin-Film for Potentiometric Hydrogen Phosphate-Ion Sensor

A cobalt-iron alloy thin-film electrode-based electrochemical hydrogen-phosphate-ion sensor was prepared by electrodepositing on an Au-coated Al2O3 substrate from an aqueous solution of metal-salts. The use of a cobalt-iron alloy electrode greatly improved the hydrogen-ion sensor response performance, i.e., the sensor worked stably for more than 7 weeks and showed a quick response time of several seconds. Among the cobalt and iron alloy systems tested, the electrodeposited Co58Fe42 thin-film electrode showed the best EMF response characteristics, i.e., the sensor exhibited a linear potentiometric response to hydrogen-phosphate ion at the concentration range between 1.0 × 10–5 and 1.0 × 10–2 M with the slope of –43 mV/decade at pH 5.0 and at 30℃. A sensing mechanism of the Co-based potentiometric hydrogen-phosphate ion sensor was proposed on the basis of results of instrumental analysis.

PREPARATION AND CHARACTERIZATION OF NOVEL CHITOSAN DERIVATIVES:ADSORPTION EQUILIBRIUM OF IRON(Ⅲ) ION

The adsorption of Fe(Ⅲ)ions from aqueous solution by chitosan alpha-ketoglutaric acid(KCTS)and hydroxamated chitosan alpha-ketoglutaric acid(HKCTS)was studied in a batch adsorption system.Experiments were carried out as function of pH,temperature,agitation rate and concentration of Fe(Ⅲ)ions.The Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms and isotherm constants were determined.The Langmuir model agrees very well with experimental data.The pseudo-first-order a...