Preconcentration of trace elements from water samples on a minicolumn of yeast (Yamadazyma spartinae) immobilized TiO2 nanoparticles for determination by ICP-AES

A trace element preconcentration procedure is described utilizing a minicolumn of yeast (Yamadazyma spartinae) immobilized TiO₂ nanoparticles for determination of Cr, Cu, Fe, Mn, Ni and Zn from water samples by inductively coupled plasma atomic emission spectrometry. The elements were quantitatively retained on the column between pH 6 and 8. Elution was made with 5% (v/v) HNO₃ solution. Recoveries ranged from 98 ± 2 (Cr) to 100 ± 4 (Zn) for preconcentration of 50 mL multielement solution (50 μg L⁻¹). The column made up of 100 mg sorbent (yeast immobilized TiO₂ NP) offers a capacity to preconcentrate up to 500 mL of sample solution to achieve an enrichment factor of 250 with 2 mL of 5% (v/v) HNO₃ eluent. The detection limits obtained from preconcentration of 50 mL blank solutions (5%, v/v, HNO₃, n = 11) were 0.17, 0.45, 0.25, 0.15, 0.33 and 0.10 μg L⁻¹ for Cr, Cu, Fe, Mn, Ni and Zn, respectively. Relative standard deviation (RSD) for five replicate analyses was better than 5%. The retention of the elements was not affected from up to 500 μg L⁻¹ Na⁺ and K⁺ (as chlorides), 100 μg L⁻¹ Ca²⁺ (as nitrate) and 50 μg L⁻¹ Mg²⁺ (as sulfate). The method was validated by analysis of freshwater standard reference material (SRM 1643e) and applied to the determination of the elements from tap water and lake water samples.     

ICP-AES determination of trace elements after preconcentrated with p-dimethylaminobenzaldehyde-modified nanometer SiO2 from sample solution

A new method that utilizes p-dimethylaminobenzaldehyde-modified nanometer SiO₂ (SiO₂-p-DMABD) as a solid phase extractant has been developed for simultaneous preconcentration of trace Cr(III), Cu(II), Fe(III) and Pb(II) prior to the measurement by inductively coupled plasma atomic emission spectrometry (ICP-AES). The preconcentration conditions of analytes were investigated, including the pH value, the shaking time, the mass of sorbent, the sample flow rate and volume, the elution condition and the interfering ions. The adsorption capacity of nanometer SiO₂-p-DMABD was found to be (mg g^− 1) Cr(III): 6.2, Cu(II): 18.6, Fe(III): 4.7 and Pb(II): 6.0 at pH 4. The adsorbed metals were quantitatively eluted with 4 mL of 1.0 mol L^− 1 HCl. According to the definition of IUPAC, the detection limits (3σ) of this method for Cr(III), Cu(II), Fe(III) and Pb(II) were 0.79, 1.27, 0.40 and 1.79 ng mL^− 1, respectively. The proposed method achieved satisfied results when it was applied to the determination of trace Cr(III), Cu(II), Fe(III) and Pb(II) in biological and water samples.     

Structure of TiO2 in TiO2-SiO2 prepared by a complexing agent-assisted sol-gel procedure

Many types of TiO₂-SiO₂ (Ti:Si=50:50 mol%) were prepared by the sol-gel procedure with and without 2-methyl-2, 4-pentanediol (MPD) as an organic ligand. The effect of MPD on the gel structure and the properties of the TiO₂ crystals were studied by XRD and raman spectroscopy, and the effect of the sol standing time on the properties of the TiO₂ crystals were also studied by XRD spectroscopy. In the gels with MPD, anatase of TiO₂ appeared at approximately 580°C, and the crystal structures were similar despite the difference in the gel preparation procedure. The titania gels with MPD were presumed to be dispersed in the silica gel matrix without any Ti-O-Si bond. In the presence of MPD, the formation of titania gels is controlled and the specified TiO₂ crystal is produced.     

Solid phase extraction and flame atomic absorption spectrometric determination of trace amounts of cadmium and lead in water and biological samples using modified TiO2 nanoparticles

A solid phase extraction procedure for the separation and preconcentration of trace amounts of Cd(II) and Pb(II) using the alizarin red S modified TiO₂ nanoparticles prior to their determination by flame atomic absorption spectrometry has been proposed. The influences of some analytical parameters such as pH, flow rates of sample and eluent, type and concentration of the eluent, and interfering ions on the recovery of Cd(II) and Pb(II) by the sorbent were investigated. The analytes were quantitatively sorbed from the aqueous solution at pH 5.5 onto a microcolumn packed with the sorbent and recovered with 2.0?mL of 1.5?mol?L^?1 hydrochloric acid. Under the optimum experimental conditions, the detection limits for Cd(II) and Pb(II) were 0.11 and 0.30?ng?mL^?1 and the relative standard deviations for ten replicate measurements of 5.0 and 50.0?ng?mL^?1 of Cd(II) and Pb(II) were 2.1 and 1.9%, respectively. A sample volume of 200?mL resulted in a preconcentration factor of 100. The method was successfully applied to the determination of Cd(II) and Pb(II) in water and biological samples, and accuracy was examined by the recovery experiments, independent analysis using electrothermal atomic absorption spectrometry, and analysis of a water standard reference material (SRM 1643e).     

Nanometer SiO2 modified with 5-sulfosalicylic acid as selective solid-phase extractant for Fe(III) determination by ICP-AES from biological and natural water samples

A new modified nanometer SiO₂ using 5-sulfosalicylic acid (SSA) as a solid-phase extractant was used for separation, preconcentration and determination of Fe(III) in aqueous solutions by inductively coupled plasma atomic emission spectrometry (ICP-AES). Its adsorption and preconcentration behaviour for Fe(III) in aqueous solutions was investigated using static procedures in detail. The optimum pH value for the separation of Fe(III) on the newly designed sorbent was 3.5. Complete elution of the adsorbed Fe(III) from the nanometer SiO₂-SSA was carried out using 2.0 mL of 0.01 mol L^− 1 of HCl. The time of 90% sorption was less than 2 min for Fe(III) at pH 3.5. Common coexisting ions did not interfere with the separation and determination of Fe(III) at pH 3.5. The maximum static adsorption capacity of the sorbent at optimum conditions was found to be 44.01 mg of Fe(III) per gram of sorbent. The relative standard deviation (RSD) of the method under optimum conditions was 3% (n = 5). The procedure was validated by analyzing three certified reference materials (GBW 08301, GBW 08504, GBW 08511), the results obtained were in good agreement with standard values. The nanometer SiO₂-SSA was successfully employed in the separation and preconcentration of the investigated Fe(III) from the biological and natural water samples yielding 100-folds concentration factor.     

Application of Dithizone-Modified TiO2 Nanoparticles in the Preconcentration of Trace Chromium and Lead from Sample Solution and Determination by Inductively Coupled Plasma Atomic Emission Spectrometry

A new method using dithizone-modified TiO₂ nanoparticles (nanometer TiO₂-DZ) as solid-phase extractant has been developed for the simultaneous preconcentration of trace amounts of chromium and lead prior to their measurement by inductively coupled plasma atomic emission spectrometry (ICP-AES). The preconcentration conditions of the analytes, including the effects of pH, sample flow rate and volume, elution conditions and interfering ions on the recovery of the analytes were investigated. At pH 5, the adsorption capacity of the nanometer TiO₂-DZ was found to be 5.8 mg g⁻¹ and 22.5 mg g⁻¹ for Cr and Pb, respectively. According to the definition of IUPAC, the detection limits (3σ) of this method for Cr and Pb were 0.38 and 1.72 ng mL⁻¹, respectively. The proposed method was applied to the determination of trace chromium and lead in foodstuffs, plants and water samples with satisfactory results.     

In situ fabrication of highly organised TiO2 nanoparticles with photo-catalytic activity in cholesterol-based organogel network

In this paper, we developed low molecular weight gel system based on cholesterol derivative containing pyridine unit attached through β-alanine linkage, which can act as efficient gelator to form novel gel systems in organic or organic–water solvents. Spherical nanoscale anatase–TiO₂ with porous structure was obtained through the in situ hydrolysis in the gel tissue upon the instant addition of water followed by calcination, which had photo catalytic activity toward naphthol blue black. To the best of our knowledge, this is the first example that cholesterol-based gel tissue was employed as the template to construct TiO₂ with photo-catalytic activity.     

Development of an on-line preconcentration system for zinc determination in biological samples

An on-line preconcentration system for zinc determination in 24-h urine, blood plasma and erythrocyte matrices by flame atomic absorption spectrometry (FAAS) was used. This procedure was based on adsorption of Zn(II) ions onto a minicolumn filled with silica gel, chemically modified with niobium(V) oxide (Nb₂O₅-SiO₂). The determination of the optimum conditions for Zn(II) preconcentration was done using two-level full factorial and Doehlert designs. In the optimization procedure, four variables (sample pH, eluent concentration, sample flow rate and eluent flow rate) were investigated. The results obtained from the full factorial design demonstrated that the sample pH and sample flow rate variables, and their interactions, were statistically significant. A Doehlert matrix was used in order to determine the optimum conditions for the sample pH and sample flow rate. The optimized conditions for sample pH and flow rate sampling were 6.6 and 7.1 ml min⁻¹, respectively, to obtain the maximum Zn(II) preconcentration and determination in the biological samples studied. Parameters of analytical curve, precision, effect of other ions in the proposed system and accuracy were achieved to assess the proposed method. The accuracy was confirmed by analysis of certified reference materials (urine Seronorm™ Trace Elements) and recovery tests in blood plasma and erythrocyte samples. Detection limit (3σ/S) of 0.77 μg l⁻¹, precision (calculated as relative standard deviation) of 1.5% for Zn(II) concentration of 10 μg l⁻¹ (n = 7) and a sampling frequency of 27 samples/h were obtained from the proposed system.     

Thermally effected structural and surface transformations of sulfated TiO2, ZrO2 and TiO2-ZrO2 catalysts

Preparations were characterized by specific surface area, thermogravimetry, and X-ray diffractometry. Thermal effects observed were (a) sulfur loss, (b) sintering, (c) crystallization and transformation of the crystalline phase(s). Thermoanalytical curves indicate that decomposition of the sulfate occurs in two distinct steps. Decrease of surface area due to (b) and (c) is concomitant to decomposition of sulfate. Sulfate was found to hinder sintering, crystallization and phase transformations of ZrO₂ and TiO₂. In low-titania and -zirconia sulfated TiO₂-ZrO₂ the minor component enhances the effect of sulfate. In equimolar TiO₂-ZrO₂ sulfate decomposition is accompanied by rapid formation of crystalline TiZrO₄.This work was supported by the MOL Rt., Hungary, which is gratefully acknowledged.     

球形TiO2-Al2O3的制备、结构和理化性能研究

将Ti(SO₄)₂溶于稀盐酸合成酸性钛溶胶，再将其与铝溶胶和六次甲基四胺溶液混合后采用油柱成型法制备了球形TiO₂-Al₂O₃复合氧化物。通过XRD、低温氮吸附-脱附与NH₃-TPD等手段对样品进行表征，结果表明600 ℃焙烧得到的球形TiO₂-Al₂O₃中TiO₂以无定型形式存在;随TiO₂含量的增加，球形TiO₂-Al₂O₃的比表面积、孔容和平均孔径呈增加趋势;TiO₂的引入没有对球形TiO₂-Al₂O₃的强酸和弱酸中心的强度产生影响，弱酸中心数量显著增加，强酸中心数量稍有增加;球形TiO₂-Al₂O₃的堆密度和压碎强度随TiO₂含量的增加而减小，颗粒直径基本保持不变。     

Visible-light-mediated facile synthesis of disulfides using reusable TiO2/MoS2 nanocomposite photocatalyst

A nontoxic and inexpensive TiO₂/MoS₂ nanocomposite was prepared and employed as an efficient photocatalyst for the synthesis of symmetrical disulfides under visible light irradiation at room temperature. Both aryl and alkyl thiols survived the reaction conditions, affording the corresponding disulfides in good to excellent yields. The photocatalyst could be easily recovered by simple centrifugation and filtration and reused several times without significant loss in its activity.     

The Preparation and Characterization of La Doped TiO2 Nanotubes and Their Photocatalytic Activity

La-doped TiO₂ nanotubes (La/TiO₂ NTs) were prepared by the combination of sol-gel process with hydrothermal treatment. The prepared samples were characterized by using transmission electron microscopy, x-ray diffraction, x-ray photoelectron spectra, and ultraviolet-visible spectra. The photocatalytic performance of La/TiO₂ NTs was studied by testing the degradation rate of methyl orange under ultraviolet (UV) irradiation. The results indicated La/TiO₂ NTs calcined at 300°C consisted of anatase as the unique phase. The absorption spectra of the La/TiO₂ NTs showed a stronger absorption in the UV range and a slight red shift in the band gap transition than that of pure TiO₂ nanotubes. The photocatalytic performance of TiO₂ NTs could be improved by the doping of lanthanum ions, which is ascribed to several beneficial effects the formation of Ti-O-La bond and charge imbalance, existing of oxygen defects and Ti³⁺ species, stronger absorption in the UV range and a slight red shift in the band gap transition, as well as higher equilibrium dark adsorption of methyl orange. 0.75 wt% La/TiO₂ NTs had the best catalytic activity.     

TiO2-polymer Nano-composites by sol-gel

Sol-gel processes make it possible to develop new hybrid electrolyte materials of the type ceramicpolymer, known as Nano-Crystallite-Insertion-Material (NCIM). They can be used in reversible alkali electrochemical cells after insertion with cations such as Li⁺. In the present study, TiO₂-polyethylene oxide hybrid materials were synthesized, from TiCl₄ and from Ti ethoxide. Their structure is analyzed in relation with the processing parameters. A primary evaluation of the nanoscale composite materials for reversible Li insertion was done.     

TiO2 nanoparticles incorporated with CuInS2 clusters: preparation and photocatalytic activity for degradation of 4-nitrophenol

TiO₂ nanoparticles incorporated with CuInS₂ clusters were prepared in a solvothermal process and characterized with X-ray diffraction (XRD), transmission electron microscopy (TEM), and energy-dispersion X-ray analysis (EDX). Compared with pure TiO₂ nanoparticles, the TiO₂ nanoparticles incorporated with CuInS₂ clusters display higher photocatalytic activity with 99.9% of degradation ratio of 4-nitrophenol after 2 h irradiation. In order to investigate the effect of the CuInS₂ clusters on the photocatalytic activity of TiO₂ nanoparticles, diffuse reflectance UV–Vis spectra (DRS), photoluminescence (PL) spectra, and photocurrent action spectra were measured. The results indicate that the enhanced photocatalytic activity is probably due to the interface between TiO₂ and CuInS₂ as a trap of the photogenerated electrons to decrease the recombination of electrons and holes.     

Effect of TiO2 Calcination Pretreatment on the Performance of Pt/TiO2 Catalyst for CO Oxidation

In order to improve the CO catalytic oxidation performance of a Pt/TiO₂ catalyst, a series of Pt/TiO₂ catalysts were prepared via an impregnation method in this study, and various characterization methods were used to explore the effect of TiO₂ calcination pretreatment on the CO catalytic oxidation performance of the catalysts. The results revealed that Pt/TiO₂ (700 °C) prepared by TiO₂ after calcination pretreatment at 700 °C exhibits a superior CO oxidation activity at low temperatures. After calcination pretreatment, the catalyst exhibited a suitable specific surface area and pore structure, which is beneficial to the diffusion of reactants and reaction products. At the same time, the proportion of adsorbed oxygen on the catalyst surface was increased, which promoted the oxidation of CO. After calcination pretreatment, the adsorption capacity of the catalyst for CO and CO₂ decreased, which was beneficial for the simultaneous inhibition of the CO self-poisoning of Pt sites. In addition, the Pt species exhibited a higher degree of dispersion and a smaller particle size, thereby increasing the CO oxidation activity of the Pt/TiO₂ (700 °C) catalyst.     

The release of TiO2 and SiO2 nanoparticles from nanocomposites

There is a growing interest in the development of nanocomposites consisting of organic polymers and TiO₂ or amorphous SiO₂ nanoparticles. These nanoparticles may be released from nanocomposites. There is evidence that amorphous SiO₂ and TiO₂ nanoparticles can be hazardous. Thus, in the design of nanocomposites with such nanoparticles, hazard reduction extending to the full nanocomposite life cycle would seem a matter to consider. Options for hazard reduction include: changes of nanoparticle surface, structure or composition, better fixation of nanoparticles in nanocomposites, including persistent suppression of oxidative damage to polymers by nanoparticles, and design changes leading to the release of relatively large particles.     

Comparison of CO2 Reduction Performance with NH3 and H2O between Cu/TiO2 and Pd/TiO2

The aim of this study is to clarify the effect of doped metal type on CO₂ reduction characteristics of TiO₂ with NH₃ and H₂O. Cu and Pd have been selected as dopants for TiO₂. In addition, the impact of molar ratio of CO₂ to reductants NH₃ and H₂O has been investigated. A TiO₂ photocatalyst was prepared by a sol-gel and dip-coating process, and then doped with Cu or Pd fine particles by using the pulse arc plasma gun method. The prepared Cu/TiO₂ film and Pd/TiO₂ film were characterized by SEM, EPMA, TEM, STEM, EDX, EDS and EELS. This study also has investigated the performance of CO₂ reduction under the illumination condition of Xe lamp with or without ultraviolet (UV) light. As a result, it is revealed that the CO₂ reduction performance with Cu/TiO₂ under the illumination condition of Xe lamp with UV light is the highest when the molar ratio of CO₂/NH₃/H₂O = 1:1:1 while that without UV light is the highest when the molar ratio of CO₂/NH₃/H₂O = 1:0.5:0.5. It is revealed that the CO₂ reduction performance of Pd/TiO₂ is the highest for the molar ratio of CO₂/NH₃/H₂O = 1:1:1 no matter the used Xe lamp was with or without UV light. The molar quantity of CO per unit weight of photocatalyst for Cu/TiO₂ produced under the illumination condition of Xe lamp with UV light was 10.2 μmol/g, while that for Pd/TiO₂ was 5.5 μmol/g. Meanwhile, the molar quantity of CO per unit weight of photocatalyst for Cu/TiO₂ produced under the illumination condition of Xe lamp without UV light was 2.5 μmol/g, while that for Pd/TiO₂ was 3.5 μmol/g. This study has concluded that Cu/TiO₂ is superior to Pd/TiO₂ from the viewpoint of the molar quantity of CO per unit weight of photocatalyst as well as the quantum efficiency.     

Selective solid-phase extraction of trace Fe(III) from biological and natural water samples using nanometer SiO2 modified with acetylsalicylic acid

A new method using acetylsalicylic acid (aspirin) modified SiO₂ nanoparticles (nanometer SiO₂-aspirin) as a solid-phase extractant (SPE) has been developed for the preconcentration of trace amounts of Fe(III) prior to their determination by inductively coupled plasma optical emission spectrometry. The preconcentration conditions of analytes were investigated, including the pH value, the shaking time, the mass of sorbent, the sample flow rate and volume, the elution condition and the interfering ions. At pH 4, the sorption capacity of nanometer SiO₂-aspirin was found to be 1.28 mmol g⁻¹. The preconcentration factor is 50. The detection limit (3σ) for Fe(III) was 0.49 ng mL⁻¹. The method was validated by analyzing two certified reference materials (GBW 08301, river sediment and GBW 08303, polluted farming soil), and the results obtained are in good agreement with standard values. The method was also applied to the determination of trace Fe(III) in biological and water samples with satisfactory results. Correspondence: Xiangbing Zhu, Department of Chemistry, Lanzhou University, Lanzhou 730000, P.R. China     

A Large-Area Patterned TiO2/SnO2 Bilayer Type Photocatalyst Prepared by Gravure Printing

Anatase TiO₂ films (thickness = 50 nm) were formed in shape of stripes (width = 1.6 mm, interval = 0.4 mm) by gravure printing on commercially available SnO₂ coated soda-lime glass substrates (dimension = 300 × 300 mm). Its photocatalytic activity was examined for the gas-phase oxidation of CH₃CHO in comparison with a simple TiO₂ photocatalyst formed on a silica glass. The patterned TiO₂/SnO₂ bilayer type photocatalyst showed a high photocatalytic activity in an H₂O bearing atmosphere. On the other hand, neither the patterning nor stacking effect was observed for the same reaction under dry conditions. These results could be explained in terms of the reducing potential of the electrons in the conduction band of the SnO₂ layer.     

Synthesis and thermal evolution of TiO2-RuO2 xerogels

Gels of the Ti Ru O system, where , 0.001, 0.01, 0.02, 0.05, 0.1, 0.15, 0.2, 0.3 and 0.5 (mol), have been synthesized by a polymeric sol-gel route from Ti (IV)-iso-propoxide and Ru (III) acetyl-acetonate (acac). The mechanisms of the hydrolysis and polycondensation reactions were studied by using Fourier Transform Infrared Spectroscopy (FTIR). The evolution of the xerogels as a function of temperature was also determined. At temperatures, as low as 200°C, mixtures of antase Ti Ru O (Ass) solid solution and rutile Ti Ru O solid solution (Rss) were attained for compositions with 0.3. For , only the anatase phase is present (A) and for , mixtures of anatase Ti Ru O (Ass) solid solution, rutile Ti Ru O solid solution (Rss) and Ru Ti O (RuO ss) solid solution were attained. RuO catalyzes the anatase to rutile transformation, even at RuO contents as low as 0.001 mol. Although, from 300 to 400°C the solid solubility of RuO into rutile-TiO phase is located at , from 500°C that value is located in the 0.05 range. This fact could be due to the metastability of the rutile solid solutions containing ruthenium oxide above 400°C. According to semiquantitative transmission electron microscopy-energy dispersive X-ray spectroscopy (TEM-EDX) analyses, at 700°C, there are compositional variations in both solid solutions, Rss and RuO ss. Thus, the system is chemically heterogeneous. The amount of Ti ions hosted into the RuO lattice in the solid solution is lower than that of Ru ions into the rutile-TiO lattice. At this temperature, the contents of these solid solutions are mol% RuO into the TiO lattice (the maximum value found) and around 8.0 mol% TiO (the maximum value found) into RuO . The RuO volatilization can promote the segregation of the ruthenium oxide giving rise to the heterogeneity and the metastability observed in this system.