Nanosecond and microsecond decay of photogenerated charges in Cd<Subscript>x</Subscript>Zn<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>S nanoparticles

The luminescent characteristics of Cd_xZn_1−xS nanoparticles were studied. It was shown that the emission is due to the recombination of holes in the valence band with electrons captured by two sorts of traps, of which the traps with lower energy were ascribed to the surface states of the Cd_xZn_1−xS nanoparticles. It was established that the Cd_xZn_1−xS nanoparticles have more pronounced ability than CdS nanoparticles to accumulate excess negative charge under the conditions of pulsed irradiation. It was shown that the consumption of the photogenerated electrons in nanosecond and microsecond time scales involves the participation of one and the same electron traps. It was established that the rate of interaction of the electrons captured by the surface traps with oxygen increases with decrease in the size of the nanoparticles. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 43, No. 5, pp. 275–281, September–October, 2007.     

Structural and optical characteristics of CdxZn1−x S nanoparticles stabilized in aqueous solutions of polymers

The structural and optical characteristics of Cd_xZn_1−xS nanoparticles, produced in aqueous solutions of sodium polyphosphate, polyvinyl alcohol, and gelatin, were studied. It was shown that the stoichiometric ratio of Cd(II) and Zn(II) in the nanoparticles can differ from that in the initial mixture. It was established that the main factors determining the final size of the Cd_xZn_1−xS nanoparticles are the nature and concentration of the polymer, the ratio of the initial concentrations of the reagents, and the temperature and duration of the post-synthesis treatment of the colloids. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 3, pp. 168–172, May–June, 2006.     

Spectral and photochemical characteristics of CdSe nanoparticles stabilized in polymer-containing media

The optical characteristics of CdSe nanoparticles, produced in aqueous solutions and polymer films in the reaction of cadmium chloride and sodium selenosulfate, were studied. The main parameters that make it possible to vary the forbidden band width were identified. The absorption, photoluminescence, Raman, and nonstationary decolorization spectra of CdSe nanoparticles of various sizes were analyzed. It was demonstrated that under the conditions of pulsed irradiation the CdSe nanoparticles are capable of accumulating excess electrons and inducing redox transformations in components of the solution (oxygen, methylviologen, and sulfite ions). __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 3, pp. 150–155, May–June, 2006.     

Ammonia gas sensor based on a spinel semiconductor,Co<Subscript>0.8</Subscript>Ni<Subscript>0.2</Subscript>Fe<Subscript>2</Subscript>O<Subscript>4</Subscript> nanomaterial

Thick film of nanocrystalline Co_0.8Ni_0.2Fe₂O₄ was obtained by sol–gel citrate method for gas sensing application. The synthesized powder was characterized by X-ray diffraction (XRD) and transmission electron microscopy. The XRD pattern shows spinel type structure of Co_0.8Ni_0.2Fe₂O₄. XRD of Co_0.8Ni_0.2Fe₂O₄ revels formation of solid solution with average grain size of about 30 nm. From gas sensing properties it observed that nickel doping improves the sensor response and selectivity towards ammonia gas and very low response to LPG, CO, and H₂S at 280 °C. Furthermore, incorporation of Pd improves the sensor response and stability of ammonia gas and reduced the operating temperature upto 210 °C. The sensor is a promising candidate for practical detector of ammonia.     

Synthesis and characterization of Pb<Subscript>1–x</Subscript>La<Subscript>x</Subscript>TiO<Subscript>3</Subscript> nanocrystalline powders

Pb_1–xLa_xTiO₃ (PLT) nanocrystalline powders were obtained by polymeric precursor method. The samples were analyzed by differential scanning calorimetry (DSC) and thermogravimetry (TG) techniques to characterize properly the distinct thermal events occurring during synthesis. The X-ray diffraction patterns show a tetragonal structure for the samples with x=0.10 and 0.15. An increase of the lanthanum concentration to x=0.20 led to a highly symmetric structure, cubic on average. The powders obtained at the end of the synthesis had an average particle size of 30 to 70 nm.     

Fabrication and characterization of TiO<Subscript>2</Subscript>–SiO<Subscript>2</Subscript> composite nanoparticles and polyurethane/(TiO<Subscript>2</Subscript>–SiO<Subscript>2</Subscript>) nanocomposite films

TiO₂–SiO₂ composite nanoparticles were prepared by a sol–gel process. To obtain the assembly of TiO₂–SiO₂ composite nanoparticles, different molar ratios of Ti/Si were investigated. Polyurethane (PU)/(TiO₂–SiO₂) hybrid films were synthesized using the “grafting from” technique by incorporation of modified TiO₂–SiO₂ composite nanoparticles building blocks into PU matrix. Firstly, 3-aminopropyltriethysilane was employed to encapsulate TiO₂–SiO₂ composite nanoparticles’ surface. Secondly, the PU shell was tethered to the TiO₂–SiO₂ core surface via surface functionalized reaction. The particle size of TiO₂–SiO₂ composite sol was performed on dynamic light scattering, and the microstructure was characterized by X-ray diffraction and Fourier transform infrared. Thermogravimetric analysis and transmission electron microscopy (TEM) employed to study the hybrid films. The average particle size of the TiO₂–SiO₂ composite particles is about 38 nm when the molar ratio of Ti/Si reaches to1:1. The TEM image indicates that TiO₂–SiO₂ composite nanoparticles are well dispersed in the PU matrix.     

Formation and properties of the Fe<Subscript>8</Subscript>V<Subscript>10</Subscript>W<Subscript>16–x</Subscript>Mo<Subscript>x</Subscript>O<Subscript>85</Subscript> type solid solution

Solid solution phases of a formula Fe₈V₁₀W_16–xMo_xO₈₅ where 0≤x≤4, have been obtained, possessing a structure of the compound Fe₈V₁₀W₁₆O₈₅. It was found on the base of XRD and DTA investigations that these solution phases melted incongruently, with increasing the value of x, in the temperature range from 1108 (x=0) to 1083 K (x=4) depositing Fe₂WO₆ and WO₃. The increase of the Mo⁶⁺ ions content in the crystal lattice of Fe₈V₁₀W₁₆O₈₅ causes the lattice parameters a=b contraction with cbeing almost constant. IR spectra of the Fe₈V₁₀W_16–xMo_xO₈₅ solid solution phases have been recorded.     

Thermo-programmed reduction study of Pt/WO<Subscript>x</Subscript>–ZrO<Subscript>2</Subscript> materials by thermogravimetry

The thermo-programmed reduction study of Pt/WO_x–ZrO₂ materials prepared with different tungsten loading were performed by thermogravimetry. The samples were synthesized by impregnation method and calcined at 600, 700 and 800°C. The characterizations of both un-calcined and calcined materials were carried out using different techniques: thermal analysis (TG and DTA), X-ray diffraction (XRD) and thermo-programmed reduction (TPR). TG and DTA analysis of un-calcined were used to determination of calcination temperatures of the samples. XRD diffractograms were useful to help us in the determination of phase presents. TPR profiles showed between three and four events at different temperatures attributed to platinum reduction and the different stages of tungsten specie reduction.     

Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/Au composite nano-particles and their optical properties

Fe₃O₄/Au composite particles with core/shell structure were prepared by reduction of Au³⁺ with hydroxylamine in the presence of an excess of Fe₃ O₄ as seeds. The resultant colloids, with an average diameter of less than 100 nm, were obtained; the remaining non-reacted Fe₃O₄ seeds can be removed by treatment with diluted HCl solution. The Fe₃O₄/Au colloids exhibit a characteristic peak of UV-visible spectra, which largely depend on the size of the particle and the suspension medium. The localized surface plasmon resonance peaks red shift and broaden with increased nanoparticle diameter or increased solvent ionic strength. The optical property is very important in the establishment of means for the detection of biomolecules.     

Structures and bonding of the complexes [M(η<Superscript>5</Superscript>-E<Subscript>5</Subscript>)] and [M(η<Superscript>5</Superscript>-E<Subscript>5</Subscript>)<Subscript>2</Subscript>] (M = Sc,Y, E = N,P): a DFT study

The mono- and bisligands complexes formed by rare earth cation (Sc, Y) with pentazolato anion or cyclo-P₅⁻ anion, the all-nitrogen counterparts of metallocenes or the all-phosphorus counterparts of metallocenes, have been studied at hybrid basis sets level with the DFT method. The geometric parameters, binding energy and the charge distributions of these complexes were characterized. And their stable orders were obtained. Monoligand complexes incline to become bisligands complexes due to their destabilization. The charge transferring between ligand and metallic cation has affinity with the stability of complex. The possibility of forming stable [M(η ⁵-E₅)₂] (M = Sc, Y, E = N, P) complexes is predicted and they are viable synthetic targets theoretically, especially Sc(η ⁵-N₅)₂.     

Facile preparation and electrochemical properties of large-scale Li<Subscript>1+<Emphasis Type="Italic">x</Emphasis></Subscript>V<Subscript>3</Subscript>O<Subscript>8</Subscript> nanobelts

Large-scale Li_1+x V₃O₈ nanobelts were successfully fabricated using filter paper as deposition substrate through a simple surface sol–gel method. The nanobelts were as long as tens of micrometers with widths of 0.4–1.0 μm and thickness of 50–100 nm. The nanobelts were characterized by X-ray diffration (XRD), Fourier infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM). The formation mechanism of the nanobelts was investigated, showing that the morphology of the nanobelts is mainly determined by the calcination temperature. Electrochemical properties of the Li_1+x V₃O₈ nanobelts were characterized by charge–discharge experiments, and the results demonstrate that the Li_1+x V₃O₈ nanobelts exhibit a high discharge capacity (278 mAh g⁻¹) and excellent cycling stability.     

Sol–gel synthesis,characterization and photocatalytic activity of mesoporous TiO<Subscript>2</Subscript>/γ-Al<Subscript>2</Subscript>O<Subscript>3 </Subscript>granules

Mesoporous TiO₂/γ-Al₂O₃ composite granules were prepared by combining sol–gel/oil-drop method, using various titania solution. The product granules can be used as a photocatalyst or adsorbent in moving, fluidized bed reactors. The phase composition and pore structure of the granules can be controlled by calcination temperature and using different titania solution. In the photocatalysis of NH₃ decomposition, TiO₂/γ-Al₂O₃ granules using Degussa P25 powder treated thermally at 450 °C showed the highest catalytic ability. However, TiO₂/γ-Al₂O₃ granules using titania made by hydrothermal method had comparable performance in NH₃ decomposition.     

Synthesis of ammonia from natural gas at atmospheric pressure with doped ceria–Ca<Subscript>3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>–K<Subscript>3</Subscript>PO<Subscript>4</Subscript> composite electrolyte and its proton conductivity at intermediate temperature

A new type of oxide–salt composite electrolyte, yttrium doped ceria YDC–Ca₃(PO₄)₂–K₃PO₄, was developed and demonstrated for its promising use for ammonia synthesis. Using this composite electrolyte, ammonia was synthesized from nitrogen and natural gas at atmospheric pressure in the solid-state proton conducting cell reactor, and the optimal condition for ammonia production was determined . The evolved rate of ammonia is up to 6.95×10⁻⁹ mol s⁻¹ cm⁻².     

Synthesis characterization and catalytic evaluation of Ni/ZrO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> aerogels catalysts

The Ni/ZrO₂/SiO₂ aerogels catalysts were synthesized via three different routes: (i) impregnation ZrO₂–SiO₂ composite aerogels with a aqueous solution of Ni(NO₃)₂, (ii) impregnation SiO₂ aerogels with a mixed aqueous solution of Ni(NO₃)₂ and ZrO(NO₃)₂ · 2H₂O, (iii) one-pot sol–gel procedure from precursors Ni(NO₃)₂/ZrO(NO₃)₂ · 2H₂O/Si(OC₂H₅)₄. These catalysts were characterized by X-ray diffraction (XRD), temperature-programmed reduction (TPR), ammonia temperature-programmed desorption (NH₃-TPD), N₂ adsorption–desorption isotherms and Fourier transform infrared (FT-IR). The Liquid-phase hydrogenation of maleic anhydride (MA) was performed over these catalysts. The results revealed that the different preparation routes result in a difference between the obtained samples, concerning the crystal structure and composition, surface acidity, mixed level of each component, texture, and catalytic selectivity.     

Sol-gel preparation and spectroscopic study of the pyrophanite MnTiO<Subscript>3</Subscript> nanoparticles

The nanosized xerogel of titanium dioxide (TiO₂) and manganese oxides (MnO₂, Mn₂O₃, Mn₃O₄) was prepared by the sol-gel method using manganese chloride (MnCl₂·4H₂O) and titanium isopropoxide (Ti(O-iPr)₄) as precursors in cetyltrimethylammonium bromide (CTAB)/ ethanol/H₂O/HCl micelle solutions, following the calcinations of the produced powders at difference temperatures. The nanostructure and phase composition of these nanoparticles were characterized with X-ray powder diffraction (XRD), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX) and X-ray photoelectron spectroscopy (XPS). The spectroscopic characterizations of these nanoparticles were also done with UV-Vis spectroscopy and laser Raman spectroscopy (LRS). XRD patterns show that the pyrophanite MnTiO₃ phase was formed at the calcinations temperature of 900°C. The TEM images show that the nanoparticles are almost spherical or slight ellipose and the sizes are 50 nm on average. The UV-Vis spectra show that the nanosized MnTiO₃ have significant absorption bands in the visible region. There are new absorption peaks of MnTiO₃ nanoparticles in LRS compared with the pure TiO₂ powder.     

Comparative study of the synthesis of CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript> and NiFe<Subscript>2</Subscript>O<Subscript>4</Subscript> in silica through the polymerized complex route of the sol–gel method

In this work the synthesis of CoFe₂O₄-SiO₂ and NiFe₂O₄-SiO₂ nanocomposites was studied via the sol–gel method, using the polymerized complex route. The polymerized precursors obtained by the reaction of citric acid, ethylene glycol, tetraethylorthosilicate, ferric nitrate, and cobalt nitrate or nickel chloride were characterized by nuclear magnetic resonance (NMR) and infrared (IR) spectroscopy. NMR and IR spectra of the precursors, without and with metallic ions, show the formation of polymeric chains with ester and ether groups and complexes of metal-polymeric precursor. The nanocomposites were obtained by the thermal decomposition of the organic fraction and characterized by X-ray diffraction (XRD) and vibrating sample magnetometry (VSM). XRD patterns show the formation of CoFe₂O₄ and NiFe₂O₄ in an amorphous silica matrix above 400 °C in both cases. When the calcination temperature was 800 °C the particle size of the crystalline phases, calculated using the Scherrer equation, reached ∼35 nm for the two oxides. VSM plots show the ferrimagnetic behavior that is expected for this type of magnetic material; the magnetization at 12.5 KOe of the CoFe₂O₄-SiO₂ and NiFe₂O₄-SiO₂ compounds was 29.5 and 17.4 emu/g, respectively, for samples treated at 800 °C.     

Preparation and selected properties of pigments on base of Ln-doped CaSnO<Subscript>3</Subscript>

Inorganic pigments containing lanthanides based on orthorhombic perovskite structure of CaSnO₃ have been prepared by solid state reaction of CaCO₃, SnO₂ and lanthanide oxides (Tb₄O₇, Pr₆O₁₁, CeO₂). The TG-DTA analysis indicates the formation of Ca-stannates around of temperature 1200°C, but from the pigmentary — application point of view, it is better to synthesize the product at higher temperature (1400 or 1500°C). The resultant materials were characterised by XRD, particle size distribution and measurement of colour properties. The doping of Ca-stannates by ions of rare earth elements (Tb, Pr, Ce) brings the production of two-and three-phase systems. The most interesting colour properties provided the stannate doped by ions of terbium and cerium and synthesized by heating at temperature 1400°C. The pigment has reddish brown colour hue.     

Preparation,Thermal Behaviour,and Crystal Structure of MgAl<Subscript>2</Subscript>F<Subscript>8</Subscript>(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>

Summary.  Single crystals of MgAl₂F₈(H₂O)₂ have been obtained under hydrothermal conditions (250°C, 14 d) from a starting mixture of AlF₃ and MgAlF₅(H₂O)₂ in a 5% (w/w) HF solution. The crystal structure has been determined and refined from single crystal data (Fmmm (#69), Z = 4, a = 7.2691(7), b = 7.0954(16), c = 12.452(2) ?, 281 structure factors, 27 parameters, R(F ² > 2σ (F ²)) = 0.0282, wR(F ² all) = 0.0885). The obtained crystals were systematically twinned according to (010/100/001) as twinning matrix, reflecting the pseudo-tetragonal metric. The crystal structure is composed of perowskite-type layers built of corner sharing AlF₆ octahedra with an overall composition of AlF₄ ⁻ which are connected via common fluorine atoms of [MgF_4/2(H₂O)_2/1] octahedra. Group-subgroup relations of MgAl₂F₈(H₂O)₂ to WO₃(H₂O)_0.33 and to other M(II)M(III)₂ F₈(H₂O)₂ structures are briefly discussed. Above 570°C, MgAl₂F₈(H₂O)₂ decomposes under elimination of water into α-AlF₃, β-AlF₃, and MgF₂. Received October 29, 2001. Accepted (revised) December 6, 2001     

Local structure and photoluminescent characteristics of Eu<Superscript>3+</Superscript> in ZnO–SiO<Subscript>2</Subscript> glasses

The photoluminescence properties of xZnO–(100−x)SiO₂ (x = 0, 5, 10, 20) containing 1% Eu₂O₃ prepared by a sol–gel method were systematically investigated. The results indicated that the relative proportion of f–f transitions to charge transfer (CT) absorption decreased with the increase of ZnO concentration. The intensity of ⁵D₀–⁷F_J transitions of Eu³⁺ ions was enhanced with the increase of ZnO content due to local structure changes and decreased quantities of Eu³⁺ ions clusters. The results of fluorescence line narrow (FLN) spectra indicated that Eu³⁺ ions occupied one site in SiO₂ glass and two sites in ZnO–SiO₂ glasses. The second-order crystal field parameters were calculated. B₂₀ and B₂₂ for site 1 increased with excitation energy, while ones hardly changed for site 2.     

Structure and Catalytic Properties of Ceria-based Nickel Catalysts for CO<Subscript>2</Subscript> Reforming of Methane

Carbon dioxide reforming (CDR) of methane to synthesis gas over supported nickel catalysts has been reviewed. The present review mainly focuses on the advantage of ceria based nickel catalysts for the CDR of methane. Nickel catalysts supported on ceria–zirconia showed the highest activity for CDR than nickel supported on other oxides such as zirconia, ceria and alumina. The addition of zirconia to ceria enhances the catalytic activity as well as the catalyst stability. The catalytic performance also depends on the crystal structure of Ni–Ce–ZrO₂. For example, nickel catalysts co-precipitated with Ce_0.8Zr_0.2O₂ having cubic phase gave synthesis gas with CH₄ conversion more than 97% at 800 °C and the activity was maintained for 100 h during the reaction. On the contrary, Ni–Ce–ZrO₂ having tetragonal phase (Ce_0.8Zr_0.2O₂) or mixed oxide phase (Ce_0.5Zr_0.5O₂) deactivated during the reaction due to carbon formation. The enhanced catalytic performance of co-precipitated catalyst is attributed to a combination effect of nano-crystalline nature of cubic Ce_0.8Zr_0.2O₂ support and the finely dispersed nano size NiO _x crystallites, resulting in the intimate contact between Ni and Ce_0.8Zr_0.2O₂ particles. The Ni/Ce–ZrO₂/θ–Al₂O₃ also exhibited high catalytic activity during CDR with a synthesis gas conversion more than 97% at 800 °C without significant deactivation for more than 40 h. The high stability of the catalyst is mainly ascribed to the beneficial pre-coating of Ce–ZrO₂ resulting in the existence of stable NiO _x species, a strong interaction between Ni and the support, and an abundance of mobile oxygen species in itself. TPR results further confirmed that NiO _x formation was more favorable than NiO or NiAl₂O₄ formation and further results suggested the existence of strong metal-support interaction (SMSI) between Ni and the support. Some of the important factors to optimize the CDR of methane such as reaction temperature, space velocity, feed CO₂/CH₄ ratio and H₂O and/or O₂ addition were also examined.