Molecularly imprinted polymer based potentiometric sensor for the determination of 1-hexyl-3-methylimidazolium cation in aqueous solution

The molecular imprinting technique is powerful to prepare functional materials with molecular recognition properties. In this work, a potentiometric sensor was fabricated by dispersing molecularly imprinted polymers (MIPs) into plasticized PVC matrix and used for the determination of 1-hexyl-3-methylimidazolium cation ([C₆mim]⁺) in aqueous solution. The MIPs were synthesized by precipitation polymerization using 1-hexyl-3-methylimidazolium chloride ([C₆mim]Cl) as the template molecule, methacrylic acid (MAA) and ethylene glycol dimethacrylat (EGDMA) as the functional monomers, and EGDMA also as the cross-linking agent. The as-prepared electrode exhibited a Nernstian response (58.87 ± 0.3 mV per decade) to [C₆mim]⁺ in a concentration range from 1.0 × 10⁻⁶ to 0.1 mol kg⁻¹ with a low detection limit of 2.8 × 10⁻⁷ mol kg⁻¹, high selectivity, and little pH influence. The as-prepared electrode was used for the detection of the [C₆mim]⁺ in distilled water, tap water, and river water with a good recovery. It was also successfully applied in the determination of mean activity coefficients of [C₆mim]Br in fructose + water systems based on the potentiometric method at 298.15 K.

     

Synthesis and characterization of a Ni/Ba2In0.6Ti1.4O5.7□0.3 cermet for SOFC application

Ni-based cermets were prepared and reduced from mixtures of NiO and Ba₂In_0.6Ti_1.4O_5.7□_0.3. A cermet containing 18.7 vol.% of Ni exhibits promising characteristics: 40% of open porosity and a lower DC resistivity than a Ni/YSZ cermet with a larger Ni content (30 vol.%). Its thermal expansion coefficient is 11.4 × 10^− 6 K^− 1 whereas that measured for Ba₂In_0.6Ti_1.4O_5.7□_0.3 is 9.9 × 10^− 6 K^− 1. Electrical measurements vs. the Ni content have shown that the percolation threshold corresponds to 15.7 vol.% of Ni. By using saccharose as a pore former, the porosity of the electrode can be tuned. It is shown that the pore size is controlled by the particle size distribution of the pore former.     

Titanium Doping to Enhance Thermoelectric Performance of 19-Electron VCoSb Half-Heusler Compounds with Vanadium Vacancies

The 19-electron VCoSb compounds are actually composites of an off-stoichiometric half-Heusler phase and impurities. Here the compositional adjustment is systematically studied in V_1−xCoSb to obtain single-phase V_0.955CoSb. Hall measurements suggest that such a V vacancy, as well as Ti doping, can optimize the carrier concentration, which decreases from ≈11.3 × 10²¹ cm⁻³ for VCoSb to ≈6.3 × 10²¹ cm⁻³ for V_0.755Ti_0.2CoSb. Low sound velocity contributes to the intrinsically low lattice thermal conductivity for VCoSb-based materials. The high Ti-dopant content results in enhanced point-defect scattering, which further decreases the lattice thermal conductivity. Finally, the optimized n-type V_0.855Ti_0.1CoSb is found to reach a peak ZT of ≈0.7 at 973 K. The work demonstrates that the VCoSb-based half-Heuslers are promising thermoelectric materials.     

Facile hydrothermal synthesis of ultrahigh-aspect-ratio V2O5 nanowires for high-performance supercapacitors

Ultrahigh-aspect-ratio V₂O₅ nanowires were successfully prepared using [VO(O₂)₂(OH₂)]⁻ as the starting material by a template-free hydrothermal route without the addition of organic surfactant or inorganic ions. The prepared samples were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer–Emmet–Teller (BET), cyclic voltammetry (CV) and galvanostatic charge–discharge (GCD). The results revealed that the peroxovanadium (V) complexes can be easily transformed to V₂O₅ nanowires by this hydrothermal route. The uniform nanowires were with width about 50 nm and length about dozens of micron. The BET analysis showed the V₂O₅ nanowires had a high specific surface area of 25.6 m² g⁻¹. The synthesized V₂O₅ nanowires performed a high capacitance of 351 F g⁻¹ when used as supercapacitor electrode in 1 mol L⁻¹ LiNO₃.     

Preparation of binder-free thin film Li4Ti5O12 anode with an adjustable thickness through anodic TiO2 nanotubes

Binder-free thickness-controllable Li₄Ti₅O₁₂ for application in lithium ion batteries was fabricated by the reaction of Li₂CO₃ and anodic nanotubular TiO₂ at 800 °C. As the concentration of Li₂CO₃ increased, the thickness of Li₄Ti₅O₁₂ film increased, leading to increase in discharge capacity. The Li₄Ti₅O₁₂ film prepared at the optimized concentration of Li₂CO₃ of 3.8 × 10^?6 mol displayed the maximum capacity of 104 μA h cm^?2 at the first cycle, which corresponds to 103 mA h g^?1. We found that excess Li₂CO₃ led to creation of LiTiO₂ phases in the Li₄Ti₅O₁₂ film, which reduced the discharge capacity. For comparison, a Li₄Ti₅O₁₂ film was prepared by the reaction of Li₂CO₃ on a non-anodized Ti foil. In this case, discharge capacity was dramatically reduced due to the formation of Li₂TiO₃ phases in Li₄Ti₅O₁₂, which was confirmed by TEM and XRD analysis.     

Performance of solid-state hybrid supercapacitor with LiFePO4/AC composite cathode and Li4Ti5O12 as anode

We report the studies on quasi-solid battery-supercapacitor (BatCap) systems fabricated using sol–gel-prepared LiFePO₄ and its composites (LACs) with activated charcoal (AC) as hybrid cathode and Li₄Ti₅O₁₂ powder as anode separator by flexible gel polymer electrolyte (GPE) film. The GPE film comprises 1.0 M lithium trifluoromethane sulfonate (LiTf) solution in ethylene carbonate (EC)–propylene carbonate (PC) mixture, immobilized poly(vinylidene fluoride-co-hexafluoro-propylene) (PVdF-HFP), which is of high ionic conductivity (∼3.8 × 10⁻³ S cm⁻¹ at 25 °C) and electrochemical stability window (∼3 V). The effect of the addition of AC in composite electrode LACs has been analyzed using various techniques such as X-ray diffraction, porosity analysis, and electrochemical methods. The interfaces of composite LACs and GPE film not only offer high rate performance but also show high specific energy (>27.8 Wh kg⁻¹) as compared to the symmetric supercapacitors and pristine lithium iron phosphate (LiFePO₄)-based lithium ion batteries. The full BatCap systems have been characterized by cyclic voltammetry and galvanostatic charge–discharge tests. The BatCap systems with composite electrodes (LACs) offer better cyclic performance as compared to that of pristine LiFePO₄-based BatCap or LIB LiFePO₄/Li₄Ti₅O₁₂.

     

Effective Mass Enhancement and Thermal Conductivity Reduction for Improving the Thermoelectric Properties of Pseudo-Binary Ge2Sb2Te5

Ge₂Sb₂Te₅ is a famous phase-change memory material for rewriteable optical storage, which is widely applied in the information storage field. The stable trigonal phase of Ge₂Sb₂Te₅ shows potential as a thermoelectric material as well, due to its tunable electrical transport properties and low lattice thermal conductivity. In this work, the carrier concentration and effective mass of Ge₂Sb₂Te₅ are modulated by substituting Te with Se. Meanwhile, the thermal conductivity reduces from 2.48 W m⁻¹ K⁻¹ for Ge₂Sb₂Te₅ to 1.37 W m⁻¹ K⁻¹ for Ge₂Sb₂Te_3.5Se_1.5 at 703 K. Therefore, the thermoelectric figure of merit zT increases from 0.24 for Ge₂Sb₂Te₅ to 0.41 for Ge₂Sb₂Te_3.5Se_1.5 at 703 K. This study reveals that Se alloying is an effective way to enhance the thermoelectric properties of Ge₂Sb₂Te₅.     

Scintillation timing characteristics of (La,Gd)2Si2O7:Ce and Gd2SiO5:Ce single crystal scintillators: A comparative study

The scintillation timing characteristics of (La,Gd)₂Si₂O₇:Ce (GPSLa23.5%:Ce) single crystal were studied and compared with Gd₂SiO₅:Ce (GSO:Ce) single crystal. The photoelectron yield, scintillation decay times and coincidence time resolution were measured. At 511 keV γ-rays, the photoelectron yield of 10,770 ± 500 phe MeV⁻¹ and energy resolution of 5.4 ± 0.2% obtained for GPSLa23.5%:Ce are much better than those of 3350 ± 160 phe MeV⁻¹ and 7.8 ± 0.3% obtained for GSO:Ce. The scintillation decay time profile was measured by the time-correlated single photon counting technique using a fast-slow coincidence setup. In both materials the comparable rise times of several nanoseconds are present. The fast component decay time of 56 ns with relative intensity of 49% obtained for GPSLa23.5%:Ce is inferior to that of 32 ns(88%) obtained for GSO:Ce. Consequently, the coincidence time resolution of GPSLa23.5%:Ce is slightly worse than that of GSO:Ce. The normalized time resolution was also discussed in terms of a number of photoelectrons and decay time of the scintillation pulse.     

Cathodic performance of V2O5 nanowires and reduced graphene oxide composites for lithium ion batteries

In this study, vanadium pentoxide (V₂O₅) nanowires (NWs) with a diameter of 100–200 nm and a length of up to several micrometers as cathode for lithium ion batteries are synthesize using an electrospinning method. The reduced graphene oxide (rGO) and V₂O₅ NWs (GVO) composites are form by wet mixing the electrospun V₂O₅ NWs and rGO. Surface morphologies, microstructure and elemental mapping, and chemical bonding states of the composites are characterize. The initial and 60 cycles discharge capacities of GVO composite composed of 1 wt% rGO show up to 225 mAh g⁻¹ and 125 mAh g⁻¹, even higher than pure V₂O₅ NWs, when the lithium ion battery cycled between 2.0 and 4.0 V with a rate of 0.2 C, because of highly conductive rGO. The GVO composite could be promising as a high performance cathode for lithium ion batteries.     

Synthesis and electrical transport properties of Lu2+xTi2−xO7−x/2 oxide-ion conductors

The Lu_2+xTi_2−xO_7−x/2 (x = 0; 0.052; 0.096; 0.286; 0.44; 0.63; 33.3–49 mol% Lu₂O₃) nanoceramics with partly disordered pyrochlore-type structure are prepared by sintering freeze-dried powders obtained by a co-precipitation technique with 1600 °C annealing. Similar to pyrochlore-like compositions in the zirconate system, some of the new titanates are good oxide-ion conductors in air. The new solid-state electrolytes have oxide-ion conductivity in the interval of 1.0 × 10^− 3 – 2.5 × 10^− 3 S/cm at 740 °C in air. This value of conductivity is comparable with that of ZrO₂/Y₂O₃ ceramics. The conductivity of Lu_2+xTi_2−xO_7−x/2 depends on the chemical composition. The highest ionic conductivity is exhibited by nearly stoichiometric Lu_2+xTi_2−xO_7−x/2 (x = 0.096; 35.5 mol% Lu₂O₃) material containing ∼ 4.8 at.% Lu_Ti anti-site defects.     

Mixed conductivity and electrocatalytic performance of SrFeO3-δ–SrAl2O4 composite membranes

Oxygen-ionic and electronic transport in dense (SrFe)_1−x(SrAl₂)_xO_z composites, consisting of strontium-deficient Sr(Fe,Al)O_3-δ and SrAl₂O₄ phases, is determined by the properties of perovskite-like solid solution. Increasing the content of SrAl₂O₄, with a total conductivity as low as 5 × 10^− 7 −  10^− 5 S × cm^− 1 at 973–1273 K in air, results in the gradual decrease of the partial conductivities, but also enables the suppression of thermal expansion. Compared to single-phase SrFe_1−xAl_xO_3-δ, (SrFe)_1−x(SrAl₂)_xO_z composites exhibit enhanced thermomechanical properties, while the oxygen permeability of these materials has similar values. The composite membranes exhibit stable performance under air/(H₂–H₂O–N₂) and air/(CH₄–He) gradients at 973–1173 K. The oxidation of dry methane by oxygen permeating through (SrFe)_0.7(SrAl₂)_0.3O_z results in dominant total oxidation, suggesting the necessity to incorporate a reforming catalyst into the ceramic reactors for natural gas conversion.     

Optical spectra and excited state relaxation dynamics of Sm<Superscript>3+</Superscript> in Gd<Subscript>2</Subscript>SiO<Subscript>5</Subscript> single crystal

Single crystals of gadolinium orthosilicate Gd₂SiO₅ containing 0.5 at% and 5 at% of Sm³⁺ were grown by the Czochralski method. Optical absorption spectra, luminescence spectra and luminescence decay curves were recorded for these systems at 10 K and at room temperature. Comparison of optical spectra recorded in polarized light revealed that the anisotropy of this optically biaxial host affects the intensity distribution within absorption and emission bands related to transitions between multiplets rather than the overall band intensity. It has been found that among four bands of luminescence related to the ⁴G_5/2→⁶H_J (J=5/2–11/2) transitions of Sm³⁺ in the visible and near infrared region the ⁴G_5/2 →⁶H_7/2 one has the highest intensity with a peak emission cross section of 3.54×10⁻²¹ cm² at 601 nm for light polarized parallel to the crystallographic axis c of the crystal. The luminescence decay curve recorded for Gd₂SiO₅:0.5 at% Sm³⁺ follows a single exponential time dependence with a lifetime 1.74 ms, in good agreement with the ⁴G_5/2 radiative lifetime τ _rad=1.78 ms calculated in the framework of Judd-Ofelt theory. Considerably faster and non-exponential luminescence decay recorded for Gd₂SiO₅:5 at% Sm³⁺ sample was fitted to that predicted by the Inokuti-Hirayama theory yielding the microparameter of Sm³⁺–Sm³⁺ energy transfer C _da=1.264×10⁻⁵² cm⁶×s⁻¹.     

Improved performance of InGaZnO thin-film transistors with Ta2O5/Al2O3 stack deposited using pulsed laser deposition

Ta₂O₅/Al₂O₃ stacked thin film was fabricated as the gate dielectric for low-voltage-driven amorphous indium–gallium–zinc-oxide (IGZO) thin film transistors (TFTs). The Ta₂O₅/Al₂O₃ stacked thin film exhibits a combination of the advantages of Al₂O₃ and Ta₂O₅. The IGZO TFT with Ta₂O₅/Al₂O₃ stack exhibits good performance with large saturation mobility of 26.66 cm² V⁻¹ s⁻¹, high on/off current ratio of 8 × 10⁷, and an ultra-small subthreshold swing (SS) of 78 mV/decade. Such small SS value is even comparable with that of submicrometer single-crystalline Si MOSFET.     

Elaboration and electrochemical characterization of LaZr2Cr4Ni5-based metal hydride alloys

The elaboration of LaZr₂Cr₄Ni₅-based intermetallic compound was performed by mechanical alloying from LaNi₅ and ZrCr₂ precursors and characterized as active materials of negative electrodes in nickel-metal hydride (Ni-MH) batteries. The effect of the milling duration on the phase composition was investigated. The structural properties of the formed phases were determined by X-ray diffraction and quantified from the Rietveld refinement data. The increase of the milling time up to 40 h leads to the highest abundance of the LaZr₂Cr₄Ni₅ phase, estimated at a weight content of 60.6 %, and a complete elimination of the LaNi₅ intermetallic precursor. The chronopotentiometry, cyclic voltammetry, and chronoamperometry techniques were applied to characterize the electrochemical behavior of prepared LaZr₂Cr₄Ni₅-based compounds. The maximum discharge capacity was 152 mAh g⁻¹, and a high electrochemical stability was obtained in the alkaline solution. The value of the hydrogen diffusion coefficient is equal to 2.1 × 10⁻⁸ cm² s⁻¹, reflecting an appropriate electrochemical hydrogenation kinetic in the LaZr₂Cr₄Ni₅-based compounds.

     

Sonocatalytic degradation of EDTA in the presence of Ti and Ti@TiO2 nanoparticles

The sonocatalytic degradation of EDTA (C₀ = 5 10⁻³ M) in aqueous solutions was studied under 345 kHz (P_ac = 0.25 W mL⁻¹) ultrasound at 22–51 °C, Ar/20%O₂, Ar or air, and in the presence of metallic titanium (Ti⁰) or core-shell Ti@TiO₂ nanoparticles (NPs). Ti@TiO₂ NPs have been obtained using simultaneous action of hydrothermal conditions (100–214 °C, autogenic pressure P = 1.0–19.0 bar) and 20 kHz ultrasound, called sonohydrothermal (SHT) treatment, on Ti⁰ NPs in pure water. Ti⁰ is composed of quasi-spherical particles (30–150 nm) of metallic titanium coated with a metastable titanium suboxide Ti₃O. SHT treatment at 150–214 °C leads to the oxidation of Ti₃O and partial oxidation of Ti⁰ and formation of nanocrystalline shell (10–20 nm) composed of TiO₂ anatase. It was found that Ti⁰ NPs do not exhibit catalytic activity in the absence of ultrasound. Moreover, Ti⁰ NPs remain inactive under ultrasound in the absence of oxygen. However, significant acceleration of EDTA degradation was achieved during sonication in the presence of Ti⁰ NPs and Ar/20%O₂ gas mixture. Coating of Ti⁰ with TiO₂ nanocrystalline shell reduces sonocatalytic activity. Pristine TiO₂ anatase nanoparticles do not show a sonocatalytic activity in studied system. Suggested mechanism of EDTA sonocatalytic degradation involves two reaction pathways: (i) sonochemical oxidation of EDTA by OH/HO₂ radicals in solution and (ii) EDTA oxidation at the surface of Ti⁰ NPs in the presence of oxygen activated by cavitation event. Ultrasonic activation most probably occurs due to the local heating of Ti⁰/O₂ species at cavitation bubble/solution interface.     

Optical Nonlinearity of Emerging ZrS2 and HfS2 Semiconductors

Compatible with existing processing technology, chemical vapor deposition method is used to synthesize ZrS₂ and HfS₂ films a a large scale. The nonlinear optical properties are characterized by Z-scan measurement with femtosecond pulses at 800 nm. The results show that saturable absorption happens in ZrS₂ owing to the larger ground state absorption than the excited state absorption, while reverse saturable absorption appears in HfS₂ due to the two-photon absorption. The figure of merit values of ZrS₂ (≈4.30 ± 0.12 × 10⁻¹⁵ esu cm) and HfS₂ (≈6.0 ± 1.4 × 10⁻¹⁵ esu cm) are much larger than those of MoS₂ and graphene in ultrafast nonlinear optical performance at the wavelength of 800 nm.     

Defect properties of Ti-doped Cr2O3

The defects in Cr_2−xTi_xO₃ (x = 0, 0.2 and 0.3) were studied by a combination of X-ray diffraction, density and electrical conductivity measurements supported by atomistic simulation. The results are consistent with the Ti being dissolved as Ti⁴⁺ compensated by Cr vacancies which associate to form complex defects of lower energy. Ti doping gives n-type semiconductivity due to a small concentration of Ti³⁺ in equilibrium with the complexes.     

Electrochemical properties of stacked-nanoflake Li4Ti5O12 spinel synthesized by a polymer-pyrolysis method

Stacked-nanoflake Li₄Ti₅O₁₂ spinel was synthesized via the pyrolysis of a Li–Ti copolymeric precursor formed by in situ polymerization of LiOH and [Ti(OC₄H₉)₄] and acrylic acid. XRD and SEM characterization shows that the powders calcined at 700 °C for 3 h was well-crystallized particles with submicron diameter. Charge–discharge measurement showed the Li₄Ti₅O₁₂ electrode had displayed excellent rate capability and delivered reversible capacity of 171, 158, 148, 138 and 99 mAh g⁻¹ at rates of 0.1C, 0.5C, 1C, 2C and 4C, respectively. The test electrode also showed excellent cyclability as the capacity retains 96.1% after 60 cycles between 0.5 and 2.5 V.     

Simultaneous hydrodynamic cavitation and glow plasma discharge for the degradation of metronidazole in drinking water

In this study, a novel hydrodynamic cavitation unit combined with a glow plasma discharge system (HC-GPD) was proposed for the degradation of pharmaceutical compounds in drinking water. Metronidazole (MNZ), a commonly used broad-spectrum antibiotic, was selected to demonstrate the potential of the proposed system. Cavitation bubbles generated by hydrodynamic cavitation (HC) can provide a pathway for charge conduction during glow plasma discharge (GPD). The synergistic effect between HC and GPD promotes the production of hydroxyl radicals, emission of UV light, and shock waves for MNZ degradation. Sonochemical dosimetry provided information on the enhanced formation of hydroxyl radicals during glow plasma discharge compared to hydrodynamic cavitation alone. Experimental results showed a MNZ degradation of 14% in 15 min for the HC alone (solution initially containing 300 × 10⁻⁶ mol L⁻¹ MNZ). In experiments with the HC-GPD system, MNZ degradation of 90% in 15 min was detected. No significant differences were observed in MNZ degradation in acidic and alkaline solutions. MNZ degradation was also studied in the presence of inorganic anions. Experimental results showed that the system is suitable for the treatment of solutions with conductivity up to 1500 × 10⁻⁶ S cm⁻¹. The results of sonochemical dosimetry showed the formation of oxidant species of 0.15 × 10⁻³ mol H₂O₂ L⁻¹ in the HC system after 15 min. For the HC-GPD system, the concentration of oxidant species after 15 min reached 13 × 10⁻³ mol H₂O₂ L⁻¹. Based on these results, the potential of combining HC and GPD systems for water treatment was demonstrated. The present work provided useful information on the synergistic effect between hydrodynamic cavitation and glow plasma discharge and their application for the degradation of antibiotics in drinking water.     

Synthesis of Gd2Ti2O7:Eu, V phosphors by sol-gel process and its luminescent properties

A red-emitting phosphor material, Gd₂Ti₂O₇:Eu³⁺, V⁴⁺, by added vanadium ions is synthesized using the sol-gel method. Phosphor characterization by high-resolution transmission electron microscopy shows that the phosphor possesses a good crystalline structure, while scanning electron microscopy reveals a uniform phosphor particle size in the range of 230-270 nm. X-ray photon electron spectrum analysis demonstrates that the V⁴⁺ ion promotes an electron dipole transition of Gd₂Ti₂O₇:Eu³⁺ phosphors, causing a new red-emitting phenomenon, and CIE value shifts to x=0.63, y=0.34 (a purer red region) from x=0.57, y=0.33 (CIE of Gd₂Ti₂O₇:Eu³⁺). The optimal composition of the novel red-emitting phosphor is about 26% of V⁴⁺ ions while the material is calcinated at 800  °C. The results of electroluminescent property of the material by field emission experiment by CNT-contained cathode agreed well with that of photoluminescent analysis.