Determination of trace impurities in titanium dioxide by slurry sampling electrothermal atomic absorption spectrometry

A slurry sampling electrothermal atomic absorption spectrometry method for the determination of Al, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Na, Ni, Pb, Sr, Tl and Zn in powdered titanium dioxide is described. The behaviour of the titanium matrix in the atomizer and its interferences with the determination of Al, Fe, Co, Ni and Mn were studied. A tungsten carbide modified graphite tube was used to improve the signal shape and the repeatability for the determination of Fe. For all elements, except for Cd and Pb, quantification by a calibration curve established with aqueous standards was possible. No chemical modifier was used throughout in order to minimize contamination. For the contamination risk elements such as Ca, Fe, K, Mg, Na and Zn, the slurry sampling technique allows to achieve limits of detection (3σ of the blank) 5–20 times lower than the solution technique, resulting for these elements in values of 1, 3, 0.5, 0.5, 0.9 and 2 ng g⁻¹, respectively, and, generally being in the range of 0.2 ng g⁻¹ (Cd) to 10 ng g⁻¹ (Al and Tl). The results obtained by the slurry sampling technique are compared with those of other independent methods including four solution methods and neutron activation analysis.     

VO2 nano-sheet negative electrodes for lithium-ion batteries

Vanadium dioxide (VO₂) nano-sheets were directly synthesized via a continuous hydrothermal process and were investigated as electrodes in a wide potential range of 0.05–3 V vs. Li/Li⁺. The nano-sheets showed excellent capacity retention, with a specific capacity of 350 mAh g^− 1 at an applied current of 0.1 A g^− 1 and 95 mAh g^− 1 at 10 A g^− 1. Further electrochemical testing suggested that a significant proportion of the charge storage in the cells was due to pseudocapacitive processes.     

Evaluation of tungsten–rhodium coating on an integrated platform as a permanent chemical modifier for cadmium,lead, and selenium determination by electrothermal atomic absorption spectrometry

A tungsten–rhodium coating on the integrated platform of a transversely heated graphite atomizer is proposed as a permanent chemical modifier for the determination of Cd, Pb, and Se by electrothermal atomic absorption spectrometry. It was demonstrated that coating with 250 μg W+200 μg Rh is as efficient as the conventional Mg(NO₃)₂+NH₄H₂PO₄ or Pd+Mg(NO₃)₂ modifiers for avoiding most serious interferences. The permanent W–Rh modifier remains stable for 300–350 firings of the furnace, and increases tube lifetime by 50%–100% when compared to pyrolytic carbon integrated platforms. Also, there is less degradation of sensitivity during the atomizer lifetime when compared with the conventional modifiers, resulting in a decreased need of re-calibration during routine analysis. The characteristic masses and detection limits achieved using the permanent modifier were respectively: Cd 1.1±0.4 pg and 0.020 μgL⁻¹; Pb 30±3 pg and 0.58 μgL⁻¹ and Se 42±5 pg and 0.64μgL⁻¹. Results from the determination of these elements in water reference materials were in agreement with the certified values, since no statistical differences were found by the paired t-test at the 95% level.     

Electronic structure and Raman spectroscopy study of dibarium magnesium orthoborate,Ba2Mg(BO3)2

The samples of dibarium magnesium orthoborate Ba₂Mg(BO₃)₂ were synthesized by solid-state reaction. The X-ray diffraction (XRD) patterns and Raman spectra of the samples were collected. Electronic structure and vibrational spectroscopy of Ba₂Mg(BO₃)₂ were systematically investigated by first principle calculation. A direct band gap of 4.4 eV was obtained from the calculated electronic structure results. The top valence band is constructed from O 2p states and the low conduction band mainly consists of Ba 5d states. Raman spectra for Ba₂Mg(BO₃)₂ polycrystalline were obtained at ambient temperature. The factor group analysis results show the total lattice modes are 5E_u + 4A_2u + 5E_g + 4A_1g + 1A_2g + 1A_1u, of which 5E_g + 4A_1g are Raman-active. Furthermore, we obtained the Raman active vibrational modes as well as their eigenfrequencies using first-principle calculation. With the assistance of the first-principle calculation and factor group analysis results, Raman bands of Ba₂Mg(BO₃)₂ were assigned as E_g (42 cm⁻¹), A_1g (85 cm⁻¹), E_g (156 cm⁻¹), E_g (237 cm⁻¹), A_1g (286 cm⁻¹), E_g (564 cm⁻¹), A_1g (761 cm⁻¹), A_1g (909 cm⁻¹), E_g (1165 cm⁻¹). The strongest band at 928 cm⁻¹ in the experimental spectrum is assigned to totally symmetric stretching mode of the BO₃ units.     

Investigation of Mg modified mesoporous silicas and their CO2 adsorption capacities

CO₂ adsorption properties on Mg modified silica mesoporous materials were investigated. By using the methods of co-condensation, dispersion and ion-exchange, Mg²⁺ was introduced into SBA-15 and MCM-41, and transformed into MgO in the calcination process. The basic MgO can provide active sites to enhance the acidic CO₂ adsorption capacity. To improve the amount and the dispersion state of the loading MgO, the optimized modification conditions were also investigated. The XRD and TEM characteristic results, as well as the CO₂ adsorption performance showed that the CO₂ adsorption capacity not only depended on the pore structures of MCM-41 and SBA-15, but also on the improvement of the dispersion state of MgO by modification. Among various Mg modified silica mesoporous materials, the CO₂ adsorption capacity increased from 0.42 mmol g⁻¹ of pure silica SBA-15 to 1.35 mmol g⁻¹ of Mg–Al–SBA-15-I1 by the ion-exchange method enhanced with Al³⁺ synergism. Moreover, it also increased from 0.67 mmol g⁻¹ of pure silica MCM-41 to 1.32 mmol g⁻¹ of Mg–EDA–MCM-41-D10 by the dispersion method enhanced with the incorporation of ethane diamine. The stability test by 10 CO₂ adsorption/desorption cycles showed Mg–urea–MCM-41-D10 possessed quite good recyclability.     

Highly active PtRuFe/C catalyst for methanol electro-oxidation

High methanol electro-oxidation activity was obtained on novel PtRuFe/C (2:1:1 at.%) catalyst. Mass and specific activities were 5.67 A  g⁻¹ catal. and 177 mA m⁻² for the PtRuFe/C catalyst while those of the commercial PtRu/C catalyst were 2.28 A g⁻¹ catal. and 87.7 mA m⁻², respectively. CO stripping results showed that on-set voltage for CO electro-oxidation was lowered by incorporation of Fe. XRD and XPS results revealed that Fe₂O₃ was formed instead of Fe(0), which resulted in large electron deficiency in Pt and easy CO electro-oxidation. The electron deficiency of Pt was proved by XPS results of Pt4f peaks, which moved to higher binding energies in PtRuFe/C than PtRu/C.     

Strong anion receptor-assisted boron-based Mg electrolyte with wide electrochemical window and non-nucleophilic characteristic

Herein we present a strong anion receptor-assisted Mg-ion electrolyte, which is synthesized from tris(2H-hexafluoroisopropyl) borate (THFPB) and MgO in 1,2-dimethoxyethane (DME). The as-prepared borate magnesium oxide complex (BMOC) electrolyte delivers exceptional electrochemical performances, including extremely high anodic stability (up to 4.2 V vs. Mg), non-corrosivity to stainless steel and aluminium foils, and reasonable ionic conductivity of 1.74 × 10^− 4 S cm^− 1. In addition, by virtue of the non-nucleophilic characteristic of the BMOC electrolyte, S ||BMOC ||Mg cells have been assembled, which show a high stable discharge capacity of 1030 mAh g^− 1 for 15 cycles and one well-defined voltage plateau of ≈ 1.1 V vs. Mg, yielding a desirable energy density beyond 1100 Wh kg^− 1 based on the weight of sulfur in cathodes.     

Electrothermal vaporization coupled with inductively coupled plasma array–detector mass spectrometry for the multielement analysis of Al2O3 ceramic powders

An electrothermal vaporization (ETV) system useful for the analysis of solutions and slurries has been coupled with a sector-field inductively coupled plasma mass spectrometer (ICP–MS) equipped with an array detector. The ability of this instrument to record the transient signals produced for a number of analytes in ETV–ICP–MS is demonstrated. Detection limits for Mn, Fe, Co, Ni, Cu, Zn and Ga are in the range of 4–60 pg μL^− 1 for aqueous solutions and in the low μg g^− 1 range for the analysis of 10 mg mL^− 1 slurries of Al₂O₃ powders. The dynamic ranges measured for Fe, Cu and Ga spanned 3–5 orders of magnitude when the detector was operated in the low-gain mode and appear to be limited by the ETV system. Trace amounts of Fe, Cu and Ga could be directly determined in Al₂O₃ powders at the 2–270 μg g^− 1 level without the use of thermochemical reagents. The results well agree with literature values for Fe and Cu, whereas deviations of 50% at the 90 μg g^− 1 level for Ga were found.     

Enhanced supercapacitive behaviors of birnessite

The birnessite type manganese dioxide electrode was prepared by the electrochemical stimulation as we recently described. It showed 190 F g⁻¹ in a Na₂SO₄ aqueous solution between −0.1 and 0.9 V versus Ag/AgCl at 1 A g⁻¹. The specific capacitance of birnessite was decreased by the manganese dissolution when the reduction and oxidation were repeated. By adding small amounts of Na₂HPO₄ or NaHCO₃ into the electrolyte, the capacitance increased to 200–230 F g⁻¹ and the manganese dissolution was successfully suppressed. Thanks to the additives, the birnessite demonstrated the much improved cycleability over >1800 cycles.     

Determination of Pt,Pd and Rh in Brassica Napus using solid sampling electrothermal vaporization inductively coupled plasma optical emission spectrometry

Conventional approaches for the analysis of platinum group elements (PGEs) in plant material suffer from sample digestion which results in sample dilution and therefore requires high sample intakes to maintain the sensitivity. The presented solid-sampling method avoids sample digestion while improving sensitivity when compared to digestion-based inductively coupled plasma optical emission spectrometry (ICP-OES) methods and allows the analysis of sample masses of 5 mg or less. Detection limits of 0.38 μg g^− 1, 0.14 μg g^− 1 and 0.13 μg g^− 1 were obtained for Pt, Pd and Rh, respectively using a sample intake of 5 mg. The reproducibility of the procedure ranged between 4.7% (Pd) relative standard deviation (RSD, n = 7) and 7.1% (Rh) RSD for 25 ng analytes. For quantification, aqueous standards were applied on paper filter strips and dried. Only the dried filters were introduced into the electrothermal vaporization unit. This approach successfully removed memory-effects observed during analysis of platinum which occurred only if liquid standards came into contact with the graphite material of the furnace. The presented method for overcoming the Pt-memory-effects may be of further interest for the analysis of other carbide-forming analytes as it does not require any technical modification of the graphite furnace (e.g., metal inlays, pyrolytic coating). Owing to lack of suitable certified reference materials, the proposed method was compared with conventional ICP-OES analysis of digested samples and a good agreement was obtained. As a result of the low sample consumption, it was possible to determine the spatial distribution of PGEs within a single plant. Significant differences in PGE concentrations were observed between the shoots (stem, leaves) and the roots. Pd was mainly found in the roots, whereas Pt and Rh were also found in higher concentrations in the shoots.     

Insoluble metal hexacyanoferrates as supercapacitor electrodes

Nano-sized insoluble iron, cobalt and nickel hexacyanoferrates (Mhcf) were prepared by a simple co-precipitation method. The potential of using these materials for supercapacitor was examined by cyclic voltammogram and constant charge/discharge. Due to the different types of the second metal (M), the Mhcf electrodes showed different electrochemical capacitive performances. The specific discharge capacitances of Fehcf, Nihcf and Cohcf electrodes at the current density of 0.2 A g⁻¹ were 425 F g⁻¹, 574.7 F g⁻¹ and 261.56 F g⁻¹, respectively. Meanwhile, the Mhcf electrodes showed good cyclic performance.     

Pseudocapacitive effect and Li+ diffusion coefficient in three-dimensionally ordered macroporous vanadium oxide for energy storage

In order to act as extrinsic pseudocapacitor materials, nanoscale vanadium oxides are required to simultaneously exhibit a capacitance-based high power density and an intercalation-based high energy density. We have fabricated a three-dimensionally ordered macroporous (3DOM) structure with a wall thickness of 14 nm that fulfills the above requirements. The 3DOM vanadium oxide film exhibits high rate performance with 355 F g^− 1 at 0.5 A g^− 1 and 125 F g^− 1 at 15 A g^− 1. The enhanced pesudocapacitive effect and Li-ion diffusion coefficient based on the 3DOM nanostructure, also contributes to the high rate capability of vanadia, which can be confirmed by cyclic voltammetry and chronoamperometry.     

Fabrication of porous Co/NiO core/shell nanowire arrays for electrochemical capacitor application

We report self-supported porous Co/NiO core/shell nanowire arrays via the combination of hydrogen reduction and chemical bath deposition methods. The Co nanowire acts as the backbone for the growth of NiO nanoflake shell forming hierarchically porous Co/NiO core/shell nanowire arrays. As electrode materials for pseudo-capacitors, the Co/NiO core/shell nanowire arrays exhibit a specific capacitance of 956 F g^− 1 at 2 Å g^− 1 and 737 F g^− 1 at 40 Å g^− 1, and good cycling stability, which is mainly due to the metal nanowire based core/shell nanowire architecture which provides good conductive network as well as fast ion/electron transfer and sufficient contact between active materials and electrolyte.     

On the electrodialysis of aqueous H2SO4–CuSO4 electrolytes with metallic impurities

This work aims to contribute to the characterization of the electrodialysis (ED) of aqueous sulfuric acid–copper sulfate solutions. The presence of impurities such as As and Sb, typical of copper electrorefining electrolytes, is also studied. Results from kinetic studies carried out in ED cells with and without re-circulation are presented. The concentrations were: 3–9 g l⁻¹ copper, 50 g l⁻¹ sulfuric acid, 3 g l⁻¹ arsenic and 0.025 g l⁻¹ antimony; the temperatures, 22 and 44 °C; the transport rates, depending on experimental conditions, 0.2–0.6 mol h⁻¹ m⁻²of membrane for copper, 0.65–2.8 for sulfate, and 0.016–0.03 for arsenic. A speciation model has been developed and applied in order to interpret the experimental results and the performance of the studied cells has been evaluated. The main conclusion is that ED can be applied to the separation and concentration of chemical species in these systems.     

Application of vapour phase calibration method for determination of sorption of gases and VOC in polydimethylsiloxane membranes

Equilibrium sorption of oxygen, carbon dioxide, ethylene, dimethyl sulphide, trichloroethylene and toluene in polydimethylsiloxane (PDMS) at 30 °C is reported. Sorption isotherms of all compounds are well described by Henry’s law within the concentration intervals studied (0.008–257 g m⁻³). Vapour phase calibration (VPC), a static headspace method, was applied instead of the usual gravimetric and barometric sorption methods. Simple, rapid and reliable determination of air-PDMS partition coefficients (S) varying between 1 and 900 (g m⁻³/g m⁻³) was achieved by this method. Solubility of toluene in PDMS was the best of all tested compounds, followed by trichloroethylene, dimethyl sulphide, ethylene, carbon dioxide and oxygen. This observed sequence can be explained by the penetrant condensability, expressed by its critical temperature (T_c). Only for ethylene, a higher solubility is measured than expected from the correlation between S and T_c. This is caused by the relative high interaction of ethylene with the polymer. The Flory–Rehner interaction parameter, χ, for ethylene was calculated 0.004 while the χ values of the other compounds varied between 0.37 and 0.80. The solubility coefficients are shown to be independent on relative air humidity. For the compounds and concentration levels studied, the sorption of dimethyl sulphide is unaffected by the simultaneous sorption of other VOC. This non-competitive behaviour is consistent with the linear partition mechanism.     

Electrochemical characterization of vertical arrays of tin nanowires grown on silicon substrates as anode materials for lithium rechargeable microbatteries

Vertical arrays of one-dimensional tin nanowires on silicon dioxide (SiO₂)/silicon (Si) substrates have been developed as anode materials for lithium rechargeable microbatteries. The process is complementary metal-oxide-semiconductor (CMOS) compatible for fabricating on-chip microbatteries. Nanoporous anodized aluminum oxide (AAO) templates integrated on SiO₂/Si substrates were employed for fabrication of tin nanowires resulting in high surface area of anodes. The microstructure of these nanowire arrays was investigated by scanning electron microscopy and X-ray diffraction. The electrochemical tests showed that the discharge capacity of about 400 mA h g⁻¹ could be maintained after 15 cycles at the high discharge/charge rate of 4200 mA g⁻¹.     

Liquid density of oxygenated additives to biofuels: 2-Butanol at pressures up to 140 MPa and temperatures from (293.15 to 393.27) K

This work reports new density data (159 points) of 2-butanol at seven temperatures between (293.15 and 393.27) K and 23 pressures from (0.1 to 140) MPa (every 5 or 10 MPa). An Anton Paar vibrating tube densimeter, calibrated with an uncertainty of ±0.7 · 10⁻³ g · cm⁻³, was used to perform these measurements. The experimental density data were fitted with the Tait-like equation with low standard deviations. In addition, the isobaric thermal expansivity and the isothermal compressibility have been derived from the Tait-like equation.     

In situ atom trapping of Bi on W-coated slotted quartz tube flame atomic absorption spectrometry and interference studies

Analytical performances of metal coated slotted quartz tube flame atomic absorption spectrometry (SQT-FAAS) and slotted quartz tube in situ atom trapping flame atomic absorption spectrometry (SQT-AT-FAAS) systems were evaluated for determination of Bi. Non-volatile elements such as Mo, Zr, W and Ta were tried as coating materials. It was observed that W-coated SQT gave the best sensitivity for the determination of Bi for SQT-FAAS and SQT-AT-FAAS. The parameters for W-coated SQT-FAAS and W-coated SQT-AT-FAAS were optimized. Sensitivity of FAAS for Bi was improved as 4.0 fold by W-coated SQT-FAAS while 613 fold enhancement in sensitivity was achieved by W-coated SQT-AT-FAAS using 5.0 min trapping with respect to conventional FAAS. MIBK was selected as organic solvent for the re-atomization of Bi from the trapping surface. Limit of detection values for W-coated SQT-FAAS and W-coated SQT-AT-FAAS was obtained as 0.14 μg mL^− 1 and 0.51 ng mL^− 1, respectively. Linear calibration plot was obtained in the range of 2.5–25.0 ng mL^− 1 for W-coated SQT-AT-FAAS. Accuracy of the W-coated SQT-AT-FAAS system was checked by analyzing a standard reference material, NIST 1643e.     

Enhanced electrochemical performance of carbon-coated TiO2 nanobarbed fibers as anode material for lithium-ion batteries

We report the electrochemical performance of carbon-coated TiO₂ nanobarbed fibers (TiO₂@C NBFs) as anode material for lithium-ion batteries. The TiO₂@C NBFs are composed of TiO₂ nanorods grown on TiO₂ nanofibers as a core, coated with a carbon shell. These nanostructures form a conductive network showing high capacity and C-rate performance due to fast lithium-ion diffusion and effective electron transfer. The TiO₂@C NBFs show a specific reversible capacity of approximately 170 mAh g^− 1 after 200 cycles at a 0.5 A g^− 1 current density, and exhibit a discharge rate capability of 4 A g^− 1 while retaining a capacity of about 70 mAh g^− 1. The uniformly coated amorphous carbon layer plays an important role to improve the electrical conductivity during the lithiation–delithiation process.     

Synthesis of coin-like hollow carbon and performance as Pd catalyst support for methanol electrooxidation

The coin-like hollow carbon (CHC) has been synthesized by only using ethanol as the carbon source with a novel Mg/NiCl₂ catalytic system via a facile solvothermal method for the first time. The CHC synthesized at optimized conditions shows an average thickness of less than 154 nm and the coin diameter of 1–3 μm. The CHC is characterized by SEM, TEM, XRD and electrochemical techniques. Pd on CHC (denotes as Pd/CHC) electrocatalysts are prepared for methanol oxidation in alkaline media. The Pd/CHC electrocatalyst gives a mass activity of 2930 A g⁻¹ Pd for methanol oxidation against 870 A g⁻¹ Pd on Pd/C electrocatalyst. One main reason for the higher mass activity of the Pd/CHC is the higher electrochemical active surface area (EASA) of the Pd/CHC.