TiO_2/EDTA-rich carbon composites:Synthesis,characterization and visible-light-driven photocatalytic reduction of Cr(Ⅵ)

Ti02/EDTA-rich carbon composites(TiO_2/EDTA-RC) have been successfully synthesized via a low temperature carbonization process. TiO_2/EDTA-RC exhibits marked absorption of visible light and excellent photoreduction of Cr(Ⅵ) activity under visible light irradiation(λ420 nm). Due to the high carboxyl group content and strong coordination ability of EDTA, TiO_2-EDTA complex can be easily fabricated between EDTA incorporated in carbon sheet and titanol group on the surface of TiO_2. TiO_2-EDTA complexes on the surface of TiO_2/EDTA-RC, the LMCT complex, are responsible for the prominent photoreduction of Cr(Ⅵ) properties of Ti02/EDTA-RC under visible light irradiation. In addition, the unique structure ofTiO_2/EDTA-RC is also propitious to the visible-light photocatalytic reduction of Cr(Ⅵ).Carbon sheet of TiO_2/EDTA-RC acts as a supporter. TiO_2 nanoparticles and EDTA homogeneously disperse into the carbon sheet supporter and form the TiO_2-EDTA complexes, which can avoid the aggregation of TiO_2 nanoparticles in the aqueous solution and provide more photocatalytic reaction points for the reduction of Cr(Ⅵ).     

In-situ reduction synthesis of manganese dioxide@polypyrrole core/shell nanomaterial for highly efficient enrichment of U(Ⅵ) and Eu(Ⅲ)

Radionuclides with long half-life are toxic,and thereby result in serious threat to human beings and ecological balance.Herein,a simple two-step synthesis method was used to prepare manganese dioxide@polypyrrole(Mn O_2@PPy)core/shell structures for efficient removal of U(Ⅵ)and Eu(Ⅲ)from aqueous solutions.The adsorption of U(Ⅵ)and Eu(Ⅲ)were investigated under different kinds of experimental conditions.The experimental results suggested that the adsorption of U(Ⅵ)and Eu(Ⅲ)on Mn O_2@PPy were greatly affected by p H.U(Ⅵ)adsorption on Mn O_2@PPy was independent of ionic strength at p H6.0,and dependent on ionic strength at p H6.0.However,Eu(Ⅲ)adsorption on Mn O_2@PPy was independent of ionic strength at the whole p H range of experimental conditions.The maximum adsorption capacities(q_(max))of U(Ⅵ)and Eu(Ⅲ)were 63.04 and54.74 mg g~(-1)at T=298 K,respectively.The BET,XRD,FTIR and XPS analysis evidenced that high adsorption capacities of U(Ⅵ)and Eu(Ⅲ)on Mn O_2@PPy were mainly due to high surface area and rich metal oxygen-containing group(i.e.,Mn–OH and Mn–O),and the interaction was mainly attributed to strong surface complexation and electrostatic interaction.This study highlighted the excellent adsorption performance of U(Ⅵ)and Eu(Ⅲ)on Mn O_2@PPy and could provide the reference for the elimination of radionuclides in real wastewater management.     

Kinetics and Mechanism of Oxidation of Lactic Acid by Dihydroxyditelluratoargentate（Ⅲ）in Alkaline Medium

The kinetics of the oxidation of lactic acid(Lac) by dihydroxyditelluratoargentate(Ⅲ）[abbreviated as DDA of Ag(Ⅲ）]anions was studied in an aqueous alkaline medium by conventional spectrophotometry in a temperature range of 25-40℃.The order of the redox reaction of lactic acid and DDA was found to be first-order.The rates increased with the increase in [OH^-]and decreased with the increase in [tellurate].No free radical was detected.In the view of this the dihydroxymonotelluratoargentate(Ⅲ）species(DMA) is assumed to be the active species.A plausible mechanism involving a two-electron transfer is proposed,and the rate equation derived from the mechanism can be used to explain all the experimenttal results.The activation parameters(25℃）and the rate constants of the rate-determining step along with the preequilibrium constants at different temperatures were evaluated.     

A highly stable membrane with hierarchical structure for wide pH range flow batteries

A membrane with high stability and ion conductivity in wide pH range is essential for energy storage devices.Here,we report a novel membrane with hierarchical core-shell structure,which demonstrates high stability and ion conductivity,simultaneously under a wide pH range applications.Spectral characterizations and theoretical calculation indicate that the non-solvent induces the chain segment configuration and eventually leads to polymer-polymer phase separation,thus forming hierarchical porous core-shell structure.Benefiting from this structure,an acidic vanadium flow battery(VFB)with such a membrane shows excellent performance over 400 cycles with an energy efficiency(EE)of above 81%at current density of 120 mA cm^-2 and an alkaline zinc-iron flow battery(AZIFB)delivers a cycling stability for more than 200 cycles at 160 mA cm^-2,along with an EE of above 82%.This paper provides a cost-effective and simple way to fabricate membranes with high performance for variety of energyrelated devices.     

REACTION KINETICS OVER PRECIPITATED Fe/Mn/K CATALYST FOR THE FISCHER-TROPSCH SYNTHESIS

The kinetics of the Fischer-Tropsch Synthesis reaction is studied in an internally recycled reactor (CSTR) over a commercial, precipitated Fe/Mn/K catalyst. Kinetic data are obtained with 1 47-4.04 H2/CO feed gas over a temperature range of 265-320℃, a pressure range of 1.0-2.6 MPa, and a space velocity range of 300-800 h-1 . The kinetic model which fits the experimental data well is the same as that of the intrinsic kinetics, i.e. -RH2 CO=kPH2PCO/(PCO bPH2O, where k is the kinetic constant for the rate-determining step and b is a function of temperature only. This model may be derived by assuming that the rate-determining step is the hydrogenation of adsorbed CO according to the enol mechanism. It is found that the CO usage ratio is probably independent of synthesis gas conversion and total pressure, and the catalyst shows high water-gas-shift activity.     

Preconcentration by Using Microcrystalline Phenolphthalein for Determining Trace Molybdenum （Ⅵ） in Water by GFAAS

Molybdenum（ Ⅵ ） is a biologically essential trace element and its role in an extremely wide variety of systems has been reported. Most common methods often fail to determine trace Mo （ Ⅵ ） in the analysis of molybdenum-containing samples, due to limitations such as inadequate detection limits and matrix interference, which make the direct determinations impossible. To solve this problem, various approaches are employed to concentrate and separate Mo（ Ⅵ ） to detectable levels. Concentration and separation methods play a main role in the analysis of trace Mo（Ⅵ）. Therefore, many separation and preconcentration procedures have been developed for the determination of Mo （ Ⅵ ）.     

Synthesis and Magnetic Properties of Fe（Ⅱ） and Nd（Ⅲ） Complexes of Poly（N-2-thiazolylacrylamide）

N-2-Thiazolylacrylamide （NTA） was polymerized by a radical route to obtain the polymer in good yield. The polymer with a pendent heterocyclic group is soluble in common organic solvents, which allow to prepare the corresponding metal complexes with higher loads easily. FTIR, ^1H NMR, elemental analysis, and energy-dispersive X-Ray spectroscopy （EDX） were applied to characterize these materials. The magnetic behavior of Fe（Ⅱ） and Nd（Ⅲ） complexes of poly（N-2-thiazolylacrylamide） was examined by a PPMS-9T magnetometer, exhibiting the characteristics of a soft ferromagnet. It is found that the Nd（Ⅲ） complex has an extremely high relative saturation magnetization of 35 emu/g.     

2-Amino-4-(4-aminophenyl)thiazole application as an ionophore in the construction of a Lu(III) selective membrane sensor

A derivative of thiazole（AAT） has been explored as a sensing material for preparation a selective Lu（III） PVC-based membrane sensor.The proposed sensor exhibits a Nernstian response over a wide concentration range from 1.0×10^-6 to 1.0×10^-1 mol/L of Lu（Ⅲ） and the detection limit is 5.7×10^-7 mol/L.The sensor response is independent of pH of the solution in the range 3.2-8.8 and possesses the advantages of fast response time（～6） and in particular,good selectivity to the lutetium ions with regard to most common metal ions,and especially all lanthanide ions.     

Direct Electrochemical Oxidation of Dihydronicotiamide AdenineDinucleotide （NADH） at An Ordered Carbon Nanotubes Electrode

With novel structure, extraordinary electronic properties, high chemical stability and extremely high mechanical strength1, carbon nanotubes (CNTs) have found a wide range of potential applications2-6. The subtle electronic properties suggest that CNTs have the ability to promote electron transfer when they are used as an electrode. The disordered CNTs have been used to fabricate electrode7-10. Thus, it is very interesting to fabricate the electrode using the ordered CNTs and to examin…     

Derivation of Martin-Hou Equation of State from Hard-particle Perturbation Theory

IntroductionIn the mid 1950's, an empirical equation of state was proposed by Martin and HouLI] abbreviated to the M--H equation. It is a more accurate equation of state applicable to real gasesincluding polar compounds, such as ammonia and water over a wide range of density and temperature. In 1981, the M--H equation was extended further to liquid domain by Hou et al. [2),and later, it was used to calculate the vapor--liquid equilibrium, liquid--liquid equilibrium andother thermodynamic p…     

Speciation Analysis of Cr(III) and Cr(VI) after Solid Phase Extraction Using Modified Magnetite Nanoparticles

A new solid phase extraction (SPE) method has been developed for the speciation of Cr(III) and Cr(VI). This method is based on the adsorption of Cr(VI) on modified alumina‐coated magnetite nanoparticles (ACMNPs). Total chromium in different samples was determined as Cr(VI) after oxidation of Cr(III) to Cr(VI) using H₂O₂. The chromium concentration has been determined by flame atomic absorption spectrometric (FAAS) technique and amount of Cr(III) was calculated by substracting the concentration of Cr(VI) from total chromium concentration. The effect of parameters such as pH, amount of adsorbent, contact time, sample volume, eluent type, H₂O₂ concentration and cetyltrimethylammonium bromide (CTAB) concentration as modifier on the quantitative recovery of Cr(VI) were investigated. Under the optimal experimental conditions, the preconcentration factor, detection limit, linear range and relative standard deviation (RSD) of Cr(VI) were 140 (for 350 mL of sample solution), 0.083 ng mL^?1, 0.1‐10.0 ng mL^?1 and 4.6% (for 5.0 ng mL^?1, n = 7), respectively. This method avoided the time‐consuming column‐passing process of loading large volume samples in traditional SPE through the rapid isolation of CTAB@ACMNPs with an adscititious magnet. The proposed method was successfully applied to the determination and speciation of chromium in different water and wastewater samples and suitable recoveries were obtained.     

Speciation of Cr(III) and Cr(VI) in Environmental Samples after Solid Phase Extraction on Amberlite XAD–2000

A method for speciation of Cr(III) and Cr(VI) in real samples has been developed. Cr(VI) has been separated from Cr(III) and preconcentrated as its pyrrolidinedithiocarbamate (APDC) complex by using a column containing Amberlite XAD–2000 resin and determined by FAAS. Total chromium has also been determined by FAAS after conversion of Cr(III) to Cr(VI) by oxidation with KMnO₄. Cr(III) has been calculated by subtracting Cr(VI) from the total. The effect of pH, flow‐rate, adsorption and batch capacity and effect of various metal cations and salt anions on the sorption onto the resin were investigated. The adsorption is quantitative in the pH range of 1.5–2.5, and Cr(VI) ion was desorbed by using H₂SO₄ in acetone. The recovery of Cr(VI) was 97 ± 4 at a 95% confidence level. The highest preconcentration factor was 80 for a 200 mL sample volume. The adsorption and batch capacity of sorbent were 7.4 and 8.0 mg g^?1 Cr(VI), respectively, and loading half time was 5.0 min. The detection limit of Cr(VI) is 0.6 μg/L. The procedure has been applied to the determination and speciation of chromium in stream water, tap water, mineral spring water and spring water. Also, the proposed method was applied to total chromium preconcentration in microwave digested moss and rock samples with satisfactory results. The developed method was validated with CRM‐TMDW‐500 (Certified Reference Material Trace Metals in Drinking Water) and BCR‐CRM 144R s (Certified Reference Material Sewage Sludge, Domestic Origin) and the results obtained were in good agreement with the certified values. The relative standard deviations were below 6%.     

Speciation of Cr(VI)/Cr(III) by electrothermal atomisation AAS after electrodeposition on a L'vov platform

Summary The pyrolysed graphite L'vov platform of a tube furnace is considered as an electrode for the electrodeposition and speciation of chromium by electrothermal atomisation atomic absorption spectrometry (ETA-AAS). Firstly, a preliminary study of the Cr(VI)/Cr(III) voltammetric behavior at pH 4.70 on a glassy-carbon electrode is carried out. Secondly, the L'vov platform is used as a cathodic macro-electrode for the selective preconcentration of Cr(VI)/Cr(III) on a mercury film. Speciation of Cr(VI)/Cr(III) is carried out on the basis of the electrolysis potential (E_e): at pH 4.70 and E_e=–0.30 V, only Cr(VI) is reduced to Cr(III) and accumulated as Cr(OH)₃ by adsorption on a mercury film; at E_e=–1.80 V both Cr(VI) and Cr(III) are accumulated forming an amalgam with added mercury(II) ions. Once the film has been formed, the platform is transferred to a graphite tube to atomise the element. The reliability of the method was tested for the speciation of chromium in natural waters and it proves to be highly sensitive thanks to the electroanalytical step. In all samples, the Cr(VI) concentration was less than the detection limit (0.15 ng ml^–1), and the concentration of Cr(III) agrees with those of total chromium. The analytical recovery of Cr(VI) added to water samples [3.50 ng ml^–1 of Cr(VI)] was 105±6.2%.     

Speciation of Cr(III) and Cr(VI) in environmental samples by using coprecipitation with praseodymium(III) hydroxide and determination by flame atomic absorption spectrometry

A speciation procedure has been established for the flame atomic absorption spectrometric determination of Cr(III) and Cr(VI) based on coprecipitation of Cr(III) by using praseodymium(III) hydroxide (Pr(OH)₃) precipitate. In the presented system, Cr(III) was quantitatively (>95%) recovered at the pH range of 10.0?C12.0 on Pr(III) hydroxide, while the recoveries of Cr(VI) were below 10%. The method was applied to the determination of the total chromium after reduction of Cr(VI) to Cr(III) by using hydroxylamine hydrochloride. The concentration of Cr(VI) is calculated by difference of total chromium and Cr(III) levels. The analytical parameters including pH of the aqueous medium, amount of Pr(III), centrifugation speed, sample volume were optimized. The influences of matrix ions were also investigated. The method was validated by the analysis of TMDA 70 fortified lake water certified reference material. The method was applied to the speciation of chromium in water samples.     

Adsorption Studies of Cr(III) & Cr(VI) on Lead Sulphide,Copper Sulphide & Zinc Sulphide-Determination Cr(III) in the Presence of Cr(VI)

Abstract

The adsorption studies of Cr(VI) in presence of Cr(III) on the sulphide of Lead, Zinc and Copper has been studied. It has been found that in case of lead sulphide 100% adsorption of Cr(VI) took place at pH 4.0 and of Cr(III) at pH 7.0. While in case of zinc sulphide the 100% adsorption of Cr(VI) took place at pH 4.5 and of Cr(III) at pH 6.5. In case of copper sulphide 100% adsorption of Cr(VI) took place at pH 5.0 and of Cr(III) at pH 7.0. This difference in adsorption at different pH values forms the basis for the determination of these ions. The method is accurate.     

Speciated isotope dilution analysis of Cr(III) and Cr(VI) in water by ICP-DRC-MS

An isotope dilution method has been developed for the speciation analysis of chromium in natural waters which accounts for species interconversions without the requirement of a separation instrument connected to the mass spectrometer. The method involves (i) in-situ spiking of the sample with isotopically enriched chromium species; (ii) separation of chromium species by precipitation with iron hydroxide; (iii) careful measurement of isotope ratios using an inductively coupled plasma mass spectrometer (ICP-MS) with a dynamic reaction cell (DRC) to remove isobaric polyatomic interferences. The method detection limits are 0.4 μg L⁻¹ for Cr(III) and 0.04 μg L⁻¹ for Cr(VI). The method is demonstrated for the speciation of Cr(III) and Cr(VI) in local nullah and synthetically spiked water samples. The percentage of conversion from Cr(III) to Cr(VI) increased from 5.9% to 9.3% with increase of the concentration of Cr(VI) and Cr(III) from 1 to 100 μg L⁻¹, while the reverse conversion from Cr(VI) to Cr(III) was observed within a range between 0.9% and 1.9%. The equilibrium constant for the conversion was found to be independent of the initial concentrations of Cr(III) and Cr(VI) and in the range of 1.0 (at pH 3) to 1.8 (at pH 10). The precision of the method is better than that of the DPC method for Cr(VI) analysis, with the added bonuses of freedom from interferences and simultaneous Cr(III) determination.     

Cr(III) and Cr(VI) Removal from Aqueous Solutions by Cheaply Available Fruit Waste and Algal Biomass

This study compared the effectiveness of different biosorbents, viz. materials commonly present in natural treatment systems (Scenedesmus quadricauda and reed) and commonly produced fruit wastes (orange and banana peel) to remove Cr(III) and Cr(VI) from a synthetic wastewater simulating tannery wastewater. The Cr(III) removal efficiency followed the order S. quadricauda?>?orange peel?>?banana peel?>?reed, whereas the Cr(VI) removal followed the order banana peel?>?S. quadricauda?>?reed?>?orange peel. The chromium biosorption kinetics were governed by the intraparticle diffusion mechanism. Isotherm data obtained using the different biosorbents were fitted to the Langmuir, Freundlich, and SIPS models, revealing that the experimental data followed most closely the monolayer sorption theory-based Langmuir model than the other models. The maximum Cr(III) sorption capacity, calculated using the Langmuir model, was found to be 12 and 9 mg/g for S. quadricauda and orange peel, respectively, and the maximum Cr(VI) sorption capacity calculated for banana peel was 3 mg/g. The influence of biosorbent size, pH, solid–liquid ratio, and competing ions were examined for Cr(III) biosorption by S. quadricauda and orange peel and for Cr(VI) sorption by banana peel. The solution pH was found to be the most influential parameter affecting the biosorption process: whereas pH 5 was found to be optimum for maximum removal of Cr(III), Cr(VI) was best removed at a pH as low as 3. Interference to chromium sorption by various ions revealed that Cr(III) binding onto orange peel occurs through electrostatic forces, whereas Cr(VI) binding onto banana peel through non-electrostatic forces.     

Electroanalytical Detection of Cr(VI) and Cr(III) Ions Using a Novel Microbial Sensor

A microbial sensor, namely carbon paste electrode (CPE) modified with Citrobacter freundii (Cf–CPE) has been developed for the detection of hexavalent (Cr(VI)) and trivalent (Cr(III)) chromium present in aqueous samples using voltammetry, an electroanalytical technique. The biosensor developed, demonstrated about a twofold higher performance as compared to the bare CPE for the chosen ions. Using cyclic voltammetry and by employing the fabricated Cf–CPE, the lowest limit of detection (LLOD) of 1x10⁻⁴ M and 5x10⁻⁴ M for Cr(VI) and Cr(III) ions respectively could be achieved. By adopting the Differential Pulse Cathodic Stripping Voltammetric technique, the LLOD could be further improved to 1x10⁻⁹ M and 1x10⁻⁷ M for Cr(VI) and Cr(III) ions respectively using the biomodified electrodes. The reactions occurring at the electrode surface‐chromium solution interface and the mechanisms of biosorption of chromium species onto the biosensor are discussed. The stability and utility of the developed biosensor for the analysis of Cr(VI) and Cr(III) ions in chromite mine water samples has been evaluated.     

Speciation of Cr(III) and Cr(VI) by Means of Melamine-Urea-Formaldehyde Resin and FAAS

 A method is described for the quantitative preconcentration and separation of trace chromium in water by adsorption on melamine-urea-formaldehyde resin. Cr(VI) is enriched from aqueous solutions on the resin. After elution the Cr(VI) is determined by FAAS. The capacity of the resin is maximal at ∼ pH 2. Total chromium can be determined by the method after oxidation of Cr(III) to Cr(VI) by hydrogen peroxide. The relative standard deviations (10 replicate analyses) for 10 mg/L levels of Cr(VI), Cr(III) and total chromium were 1.5, 3.5 and 2.8% respectively. The procedure has been applied to the determination and speciation of chromium in lake water, tap water and chromium-plating baths.     

Effect of Light on the Electrokinetic Behavior of TiO(2) Particles in Contact with Cr(VI) Aqueous Solutions

The electrokinetic behavior of titanium dioxide particles (Degussa P25, mainly composed of anatase) put in contact with chromium(VI) aqueous solutions is highly sensitive to light exposure under normal laboratory conditions. In the dark, adsorption of Cr(VI) gives rise to substantial decrements in the mobilities, especially in the acidic branch, and, at higher concentrations, to shifts in the isoelectric point (pH(piep)) to lower values, as expected for anionic chemisorption. A two-mode adsorption model accounts qualitatively for the results. Under light, pH(piep) shifts in the opposite direction as the Cr(VI) concentration increases. A maximum value is attained at [Cr(VI)] approximately 10(-3) mol dm(-3), pH(piep) 8.2, which coincides with values reported for hydrous chromium(III) oxides. At higher concentrations, Cr(VI) adsorption defines a shift of pH(piep) to lower values. It is concluded that light absorption by titanium dioxide promotes the reduction of Cr(VI) and the surface precipitation of the hydrous Cr(III) oxide. The values of pH(piep) for partially covered surfaces are well described by a simple model of surface ionization derived earlier. FTIR/ATR analysis of the surfaces supports this interpretation, and further suggests that one of the modes of Cr(VI) adsorption implies surface dimerization to yield adsorbed dichromate. Copyright 2000 Academic Press.