Catalytic-kinetic spectrophotometric determination of vanadium （V） based on the Celestine blue-bromate-vanadium （V）-citric acid reaction

A novel sensitive and relatively selective kinetic method is presented for the determination of V(V) based on its catalytic effect on the oxidation reaction of Celestine blue by potassium bromate in the presence of citric acid as an activator.The reaction was monitored spectrophotometrically by measuring the decrease in absorbance of Celestine blue at a maximum absorption wavelength of 540 nm between 0.5 and 9 min(the fixed-time method) in an H3PO4 medium at 45°C.The effect of various parameters such as con...     

Solid-phase extraction of trace Au(Ⅲ) with SDG and determination by the catalytic spectrophotometric method

The new catalytic kinetic spectrophotometric method for Au(Ⅲ) determination was developed and validated.It was based on the catalytic effect of gold on the oxidation of sudan red Ⅲ by ammonium peroxodisulfate ((NH4)2S2O8) with nitrilo triaeetic acid as an activator in microemulsion and H2SO4 medium.Under optimum conditions,there was the linearity of the calibration curve in the concentration range from 0 to 20 μg/L Au(Ⅲ) at 520 nm.The relative standard deviation was 3.0% with a correlation coefficient of 0.9986.The detection limit achieved was 9.75×10-5 μg/mL.A new method using a column packed with sulfhydryl dextrose gel (SDG) as a solid-phase extraetant has been developed for the preeoncentration and separation of Au(Ⅲ) ions.The method has been applied to the determination of trace gold with satisfactory results.     

Micellar sensitized catalytic kinetic spectrophotometry for highly accurate and reproducible determination of Ⅴ(Ⅳ) and Ⅴ(Ⅴ)

A highly accurate and reproducible micellar sensitized kinetic method was proposed for determination of V(VI). The method is based on its catalytic effect on the oxidation of Coomassie brilliant blue R 250(CBB?) by bromate at pH 2.0. The reaction was monitored spectrophotometrically by measuring absorbance change with a fixed-time method of 5 min at 594 and 552 nm with and without surfactant. The variables influencing the calibration sensitivity were extensively investigated, and the optimal conditions were established. The linear calibration range was 10–1,600 lg L-1with a relative SD ranging from 0.35 % to 3.35 %(for five replicate measurements of75, 500, 1,000, and 1,500 lg L-1) and a detection limit of3.8 lg L-1. The selectivity was also investigated, and greatly enhanced by suitable masking agents. The method was successfully applied to the analysis of V(IV) in presence of excess V(V) up to 25 fold in environmental waters with the recoveries of 100.0 %–102.8 % for V(IV) and95.7 %–99.7 % for total V. Its accuracy was validated by analysis of certified reference material via the present kinetic method and standard flame atomic absorption spectrometric method after extractive preconcentration with good agreement between certified and found values.     

Solid-phase extraction of trace Au（Ⅲ） with SDG and determination by the catalytic spectrophotometric method

The new catalytic kinetic spectrophotometric method for Au(III) determination was developed and validated. It was based on the catalytic effect of gold on the oxidation of sudan red III by ammonium peroxodisulfate ((NH4)2S2O8) with nitrilo triacetic acid as an activator in mi- croemulsion and H2SO4 medium. Under optimum conditions, there was the linearity of the calibration curve in the concentration range from 0 to 20 μg/L Au(III) at 520 nm. The relative standard deviation was 3.0% with a correlation coefficient of 0.9986. The detection limit achieved was 9.75 × 10-5 μg/mL. A new method using a column packed with sulfhydryl dextrose gel (SDG) as a solid-phase extractant has been developed for the preconcentration and separation of Au(III) ions. The method has been applied to the determination of trace gold with satisfactory results.     

Dual-wavelength dual-indicator catalytic kinetic spectrophotometry for determination of trace Ru(III)

A new dual-wavelength dual-indicator catalytic kinetic spectrophotometric method for the determination of trace Ru(III)was studied.This method was based on Ru(III)-catalyzing oxidation of Arsenazo I and indigo carmine by potassium bromate in sulfuric acid.The absorbances of the catalytic and noncatalytic systems were measured at 510 and610 nm,respectively.Under the optimum conditions,the linear range of determination is 0–0.12 lgáml-1and the detection limit is 1.21 9 10-4lgáml-1.The method was applied for the determination of trace Ru(III)in ore samples with satisfactory results.     

Micellar sensitized catalytic kinetic spectrophotometry for highly accurate and reproducible determination of V（IV） and V（V）

A highly accurate and reproducible micellar sensitized kinetic method was proposed for determination of V（VI）. The method is based on its catalytic effect on the oxidation of Coomassie brilliant blue R 250 （CBB＋） by bromate at pH 2.0. The reaction was monitored spectro- photometrically by measuring absorbance change with a fixed-time method of 5 min at 594 and 552 nm with and without surfactant. The variables influencing the calibra- tion sensitivity were extensively investigated, and the optimal conditions were established. The linear calibration range was 10-1,600 μg.L-1 with a relative SD ranging from 0.35 % to 3.35 % （for five replicate measurements of 75, 500, 1,000, and 1,500 μg.L-1） and a detection limit of 3.8 μg.L-1. The selectivity was also investigated, and greatly enhanced by suitable masking agents. The method was successfully applied to the analysis of V（IV） in pre- sence of excess V（V） up to 25 fold in environmental waters with the recoveries of 100.0 %-102.8 % for V（IV） and 95.7 %-99.7 % for total V. Its accuracy was validated by analysis of certified reference material via the present kinetic method and standard flame atomic absorption spectrometric method after extractive preconcentration with good agreement between certified and found values.     

Determination of trace amounts of silver(I) in the presence of an activator with a kinetic method

A simple and sensitive kinetic-spectrophotometric method was developed for the determination of trace amounts of silver, based on its catalytic effect on the oxidation of azocarmine G by peroxydisulfate in sulfuric acid medium and at 30 °C in the presence of 1,10-phenantroline as activator. The absorbance was measured at 525 nm with the fixed-time method. The optimization of the operating conditions regarding concentrations of the reagents, temperature, ionic strength, and interferences was also investigated. The calibration curve is linear over the concentration range 0.3–50.0 ng ml-1of silver with good precision and accuracy, and the detection limit is down to0.125 ng ml-1. The relative standard deviation for a standard solution of 25.0 ng ml-1of silver is 1.36 %(n = 10).The proposed method proves to be highly sensitive,selective, and relatively rapid for the assay of silver at lowlevel range of 0.3–50.0 ng ml-1without any pre-concentration and separation step. The method was applied for the determination of silver in river water and white photographic film. The analytic results of the real samples are in excellent agreement with atomic absorption spectrometry analysis. The analytical results obtained are satisfactory.     

Electrodeposition mechanism of ZnSe thin film in aqueous solution

ZnSe is one of the important and excellent Ⅱ-Ⅵsemiconductor materials, which has direct transition band structure. In this paper, ZnSe thin films were prepared by an electrochemical deposition method, and the formation mechanism of ZnSe was studied systematically. Voltammetry and chronoamperometry combined with X-ray diffraction(XRD) and Raman techniques were used to analyze the deposition processes. It is found that the substrate and deposition potentials have a great influence on the phase composition of deposited thin film, and Zn substrate is beneficial to the preparation ZnSe films. Strong selenium-substrate interaction results in the formation of selenium compounds involving electrode materials. The addition of Zn(Ⅱ) source can affect the reduction potential of Se, and results in the change of reducing mechanism of Se(0) from Se(Ⅳ). Se(0) formed from H_2Se because the formation of H_2Se is more active than forming Se(0)directly from Se(Ⅳ), and H_2Se can recombine with the substrate material, forming selenium-substrate compounds more quickly.     

Determination of trace gadolinium by catalytic kinetic fluorimetry

There was a significant catalytic effect of trace Gd(III) ions on the oxidative reaction of potassium persulfate with Saffron T in the acetic acid–sodium acetate buffer solution. Thus, a catalytic kinetic fluorimetry method for the determination of trace Gd(III) ions was established. The factors such as acidity, concentration of reagents, reaction time, and temperature as well as influence of coexisting ions were discussed. The optimum reaction conditions were established. The apparent rate constant and apparent activation energy of the reaction were determined. The linear range is 0.02–0.10 lgáml-1,and the detection limit is 7.27 9 10-4lgáml-1. This method was used for the determination of gadolinium in the samples of lanthanum acetate with RSD of 0.9 %–3.1 %.     

Inorganic shell nanostructures to enhance performance and stability of metal nanoparticles in catalytic applications

In this article, we review the recent progress and our research activity on the synthesis of inorganic shell nanostructures to enhance the catalytic performance and stability of metal nanoparticles in catalytic applications.First, we introduce general synthetic strategies for the fabrication of inorganic nanoscale shell layers, including template-assisted sol-gel coating, hydrothermal(or solvothermal) synthesis and the self-templating process.We also discuss recent examples of metal nanoparticles(NPs) with nanoscale shell layers, namely core–shell, yolk–shell and multiple NPs-embedded nanoscale shell. We then discuss the performance and stability of metal particles in practical catalytic applications. Finally, we conclude with a summary and perspective on the further progress of inorganic nanostructure with nanoscale shell layers for catalytic applications.     

Catalytic spectrophotometric determination of trace vanadium in fly ash and coal gangue by Triton X-100 enhancing effect

Trace V(V) catalyzes mightily the decolorization reaction of arsenazo Ⅲ(AsA Ⅲ) by oxidizing with H2O2 in a pH 4.0 HAc-NaAc buffer solution, and the addition of Triton X-100 can further increase the sensitivity of the reaction and its catalytic extent is linear with the content of V(V). A catalytic spectrophotometric procedure for determining trace V(V)was developed. The results show that the maximun absorption of the color solution is at 560 nm and the detection limit of the method for V(V) is 0.014 mg.L-1. Beer's law is obeyed for V(V) in the range of 0.00-0.20 mg.L-1. The recoveries are 99.0%-104.6%, and the relative standard deviations (RSD) are 2.7%-3.7%. Combined with ion-exchange resin, the method has been applied to the determination of trace vanadium in fly ash and coal gangue with satisfactory results.     

Catalytic spectrophotometric determination of trace vanadium in fly ash and coal gangue by Triton X-1O0 enhancing effect

Trace Ⅴ(Ⅴ) catalyzes mightily the decolorization reaction of arsenazo Ⅲ(AsA Ⅲ) by oxidizing with H2O2 in a pH 4.0 HAc-NaAc buffer solution, and the addition of Triton X-100 can further increase the sensitivity of the reaction and its catalytic extent is linear with the content of Ⅴ(Ⅴ). A catalytic spectrophotometric procedure for determining trace Ⅴ(Ⅴ)was developed. The results show that the maximun absorption of the color solution is at 560 nm and the detection limit of the method for Ⅴ(Ⅴ) is 0.014 mg.L^-1. Beer‘s law is obeyed for Ⅴ(Ⅴ) in the range of 0.00-0.20 mg.L^-1.The recoveries are 99.0%-104.6%, and the relative standard deviations (RSD) are 2.7%-3.7%. Combined with ion-exchange resin, the method has been applied to the determination of trace vanadium in fly ash and coal gangue with satisfactory results.     

Analysis of trace mercury in water by solid phase extraction using dithizone modified nanometer titanium dioxide and cold vapor atomic absorption spectrometry

A new method for analysis of trace mercury in water samples was developed, based on the combination of preconcentration/separation using dithizone-modified nanometer titanium dioxide (TiO2) as a solid phase extractant and determination by cold vapor atomic adsorption spectrometry (CVAAS). Dithizone was dissolved with alcohol and loaded on the surface of nano-sized TiO2 powders by stirring. The static adsorption behavior of Hg2 on the dithizone-modified nanoparticles was investigated in detail. It was found that excellent adsorption ratio for Hg2 could be obtained in the pH range of 7-8 with an oscillation time of 15 min, and a 5 mL of 3.5 mol·L-1 HCl solution could quantitatively elute Hg2 from nanometer TiO2 powder. Common coexisting ions caused no obvious influence on the determination of mercury. The mechanisms for the adsorption and desorption were discussed. The detection limit (3σ) for Hg2 was calculated to be 5 ng·L-1. The proposed method was applied to the determination of Hg2 in a mineral water sample and a Zhujiang River water sample. By the standard addition method, the average recoveries were found to be 94.4%-108.3% with RSD (n = 5) of 2.9%-3.5%.     

Fluorescence determination of platinum with dibromohydroxyphenyl-fluorone in microemulsion after separation and enrichment by sulfhydryl dextrose gel

A new fluorescence quenching method has been developed for the determination of platinum in nonionic mieroemulsion medium.This method is based on the fact that platinum can form a stable chelate with dibromohydroxyphenyl-fluorine (DBHPF) when they are in the molar ratio of 12 in the nonionic microemulsion medium.Under optimum conditions,the system,having the maximum excitation and emission wavelengths at 468 nm and 532 nm,respectively,shows constant fluorescence intensity in the pH range of 3.5-4.0 and high selectivity and sensitivity as well as low interference from foreign ions.Furthermore,this fluorescence intensity is a linear function of Pt(Ⅳ) concentration in the range of 0.002-1.00 μg·mL-1 and the limit of detection is 2.90 ng·mL-1.     

In situ growth of NiSe@Co_(0.85)Se heterointerface structure with electronic modulation on nickel foam for overall water splitting

Constructing heterointerface engineering has becoming an effective and general strategy for developing highly efficient and durable nonnoble electrocatalysts for catalyzing both hydrogen evolution reaction(HER) and oxygen evolution reaction(OER).In this work,we synthesized a self-supporting heterogeneous NiSe@Co_(0.85)Se/NF electrocatalyst using a facile in situ selenization of transition metal precursors that coated on the nickel foam(NF) in polyol solution.The NF was used as both conductive substrate and nickel source,ensuring superior electronic conductivity for catalyzing.The NiSe@-Co_(0.85)Se/NF exhibited remarkable bifunctional electrocatalytic activities with HER overpotential of 168 mV and OER overpotential of 258 mV to achieve 10 mA·cm~(-2).The water splitting system using NiSe@Co_(0.85)Se/NF as both anode and cathode electrodes achieved a current density of 10 mA·cm~(-2) at 1.61 V with nearly 100% faradaic efficiency and impressively long-term stability.The efficient bifunctional catalytic performance of NiSe@-Co_(0.85)Se/NF should be attributed to the electronic modulation and synergistic effect between NiSe and Co_(0.85)Se,the intrinsic metallic conductivity and the enlarged active sites exposure.This work provides a facile method for developing heterogeneous bifunctional catalysts for advanced electrochemical energy conversion technologies.     

Formation and in vitro induction ability of apatite nanobelt coating on silicon

Apatite coating with nanobelt structure was fabricated on single crystal silicon by a two-step method of electrodeposition at 1.0-2.0 mA/cm2 with DC power and vapor-thermal treatment(VTT) at 150-180℃ for 6 h over alkali medium.Scanning electron microscopy(SEM),X-ray diffractometry(XRD),and electron diffraction spectrometry(EDS) were employed to investigate the compositions and morphologies of specimens before or after vapor-thermal treatment.The results demonstrate that nanobelt crystals of coating,0.5-2 μm in width,100 nm in thickness,and 6-10 μm in length,are Ca-deficient apatite(CDA) with a mole ratio of Ca to P approximately of 1.60,which shows similarity of the nanobelt coating to inorganic phase in composition and to collagen in dimension appearing in human hard tissue.Induced nucleation and growth of bone-like apatite were observed on the nanobelt after soaking in a simulated body fluid(SBF) for 6 h and for 3 d,respectively,identifying that nanobelt has good ability for induction of bone-like apatite in SBF.     

Extraction equilibria and kinetics of Ti(Ⅳ) from leached chloride liquors of ilmenite

Extraction of titanium(Ⅳ)from real chloride leach liquor of ilmenite was carried out with 0.1 mol L~(-1)di-(2-ethylhexyl)phosphoric acid(HDEHP)in kerosene.Equilibrium and kinetics studies for Ti(Ⅳ)were carried out in the presence of impurities that were leached with Ti(Ⅳ).Parameters affecting extraction rate of Ti(Ⅳ)from chloride media in the presence of Fe(Ⅲ),Mg(Ⅱ),and Al(Ⅲ)were studied to evaluate the stoichiometry of extracted Ti(Ⅳ)species.It is found that the extraction rate of Ti(Ⅳ)is dependent on the extractant concentration and pH of solution.Under the optimum conditions,more than 95%Ti(Ⅳ)can be extracted.On the basis of slope analysis method,the extracted species of Ti(Ⅳ)appears to be[TiO(H_2A_2)_2]_(org),where H_2A_2 refers to HDEHP.Further,the kinetic studies of the extraction process of Ti(Ⅳ)and other metal ion impurities were carried out by a Lewis cell with a constant interfacial area of 16.7 cm~2.Analysis of the experimental results suggests that TiO~(2+)extraction rate by HDEHP is the first with respect to hydrogen ion concentration and HDEHP concentration.The results are interpreted by a reaction mechanism where the extraction process is controlled by a diffusion process at the interface rather than in the bulk phase.     

Flow-injection spectrophotometric determination of vanadium with malachite green oxalate by bromate in acidic and micellar medium

A flow injection method is proposed for determining vanadium(V). The method is based on its catalytic effect on the oxidation of malachite green oxalate by bromate. The reaction was monitored spectrophotometrically by measuring malachite green oxalate absorbance at λmax = 625 nm. The reagents and manifold variables, which have influences on the sensitivity, were investigated and the optimum conditions were established. The optimized conditions made it possible to determine vanadium in the ranges of 10-140 ng/mL with a detection limit of 5.2 ng/mL and a sample rate of 20 ± 5 samples/h.     

4-methoxy-2,6-bis(3,5-dimethylpyrazoyl)-1,3,5-triazine modified carbon paste electrode for trace Cu(Ⅱ) determination by differential pulse volt-ammetry

A differential pulse voltammetric method was developed for the sensitive and selective determination of Cu(Ⅱ) at 4-methoxy-2,6-bis(3,5-dimethylpyrazoyl)-l,3,5-triazine modified carbon paste electrode in 0.05 mol/L KHC8H4O4 solution (pH = 4.02). The oxidation peak of Cu(Ⅱ) was observed at 0.065 V(vs Ag/AgCl) by scanning the potential in positive direc-tion. The analysis procedure consisted of an open circuit accumulation step in stirred sample solution. It was followed by medium exchange to a clean solution and subsequently an anodic potential scan was affected to obtain the voltammetric peak. The current was proportional to the concentration of the Cu(Ⅱ) ion in a range of 1× 10-7-1×10-4 mol/L for 6 min accumulation; the most of metal ions did not interfere with the determination. The developed method was applied to Cu(Ⅱ) determination in coal-ash sample, the results agreed with that of atomic adsorption spectroscopy(AAS).     

Hierarchical porous carbon derived from animal bone as matric to encapsulated selenium for high performance Li-Se battery

Animal bone was employed as raw material to prepare hierarchical porous carbon by KOH activation. Rare metal selenium(Se) was encapsulated into hierarchical porous carbon successfully for the cathode material of Li–Se battery, achieving the transformation of waste into energy,protecting environment and reducing the spread of the disease. Animal bone porous carbon(ABPC) acquires a specific surface area of 1244.7903 m~2·g~(-1) and a pore volume of 0.594184 cm~3·g~(-1). The composite Se/ABPC with 51 wt%Se was tested as a novel cathode for Li–Se batteries. The results show that Se/ABPC exhibits high specific capacity,good cycling stability and current-rate performance; at 0.1C,the composite Se/ABPC delivers a high reversible capacity of 705 mAh·g~(-1) in the second cycle and 591 mAh·g~(-1) after 98 cycles. Even at the current density of 2.0C, it can still maintain at a reversible capacity of 485 mAh·g~(-1). The excellent electrochemical properties benefit from the high electron conductivity and the carbon with unique hierarchical porous structure. ABPC can be a promising carbon matrix for Li–Se batteries.