The influence of sucrose on the crystallization behaviour in the system CaO-SiO2-C12H22O11-H2O under hydrothermal conditions

Hydrothermal synthesis in the presence of sucrose has been carried out at 200 °C and autogeneous pressure in the system CaO-SiO₂-C₁₂H₂₂O₁₁-H₂O to investigate the influence of C₁₂H₂₂O₁₁ on phase formation and the crystal habit of calcium silicate hydrates (CSH-phases). A sucrose/lime ratio of 0.5 was utilized in all experiments and the reactivity of the SiO₂ source was varied using educts of different grain size of ∼40 mesh and >230 mesh. CaO/SiO₂ concentration ratios of 0.5 and 0.8 have been selected, the latter with respect to the composition of the important CSH-phase 11 Å tobermorite. The results were compared with experiments under similar but sucrose-free conditions. X-ray powder diffraction (XRD), scanning electron microscopy (SEM) combined with energy dispersive X-ray analysis (EDX-analysis) as well as Fourier transform infrared spectroscopy (FTIR-spectroscopy) have been applied for analyses.A retarding effect of sucrose on CSH-phase formation has been observed. Only minor amount of CSH without regular morphology was observed instead of typically fibrous 11 Å tobermorite formed in the sucrose-free system. Sucrose altered the reaction mechanism in the CSH-system and hydrothermal process started with rapid reaction of sucrose and lime. The further course of crystallization was dominated by an extended precipitation of calcium carbonate and small amounts of calcium oxalate hydrate. Formation of these stable hydrothermal decomposition products of saccharated lime is strongly suppressing the CSH-crystallization.     

Hydrothermal synthesis of nanocrystalline VO2 from poly(diallyldimethylammonium) chloride and V2O5

Novel vanadium dioxide nanorods were fabricated from V₂O₅ in the presence of a reducing agent, the poly(diallyldimethylammonium chloride) (PDDA) via a hydrothermal method at 180 °C for 48 h. The samples produced were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), infrared spectroscopy (FTIR), nitrogen adsorption (BET) and thermogravimetry (TG/DTG). The nanorods obtained are approximately 50 nm wide and from 300 to 500 nm long and presents high surface area (42 m² g⁻¹). The nanocrystalline B phase VO₂ is not produced by hydrothermal treatment in the absence of the PDDA polyelectrolyte.     

Synthesis, structure and ion exchange properties of 11 Å tobermorites from newsprint recycling residue

Al-substituted 11 Å tobermorites were obtained from stoichiometrically adjusted mixtures of newsprint recycling waste, sodium silicate and calcium oxide via hydrothermal synthesis at 100 °C. Hydrothermal processing in water yielded a highly crystalline 11 Å tobermorite product with a Cs⁺ cation exchange capacity of 85 meq 100 g⁻¹ and selective Cs⁺ distribution coefficient of ∼5500 cm³ g⁻¹. Conversely, a product of inferior crystallinity was obtained from hydrothermal synthesis in alkaline liquor whose Cs⁺ ion exchange capacity and selective Cs⁺ distribution coefficient were found to be 66.3 meq 100 g⁻¹ and ∼700 cm³ g⁻¹, respectively. Silicate chain configuration was found to have a modest impact on the number of cation exchange sites per unit cell, whereas the influence of structural defects on selectivity was more pronounced. The structures and ion exchange credentials of both 11 Å tobermorite products corresponded well with those of their essentially phase-pure counterparts.     

Synthesis of layered sodium lanthanum selenide through ion exchange reactions

Layered hexagonal KLaSe2 (α-NaFeO₂-type) was synthesized using the reactive flux method and analyzed by powder XRD to determine its lattice constants (space group R-3m, a = 4.40508(5) Å, c = 22.7838(5) Å). NaLaSe₂, which normally crystallizes as a disordered rock salt structure with mixed Na+/La + 3 sites, was synthesized through a solid state ion exchange reaction at 585 °C from a 1:3 molar ratio mixture of KLaSe₂:NaI. The product of this reaction was hexagonally layered NaLaSe₂ (space group R-3m, a = 4.3497(3) Å, c = 20.808(2) Å) isostructural to KLaSe₂. This product was analyzed by comparison with members of the set of solid solutions Na_(1−x)K_(x)LaSe₂ to confirm that the extent ion exchange in this reaction was complete. Cubic (disordered) NaLaSe₂ was also reacted with KI to yield the poorly crystalline hexagonally layered product with the approximate formula Na_0.79K_0.21LaSe₂.     

Hydrothermal synthesis attempts of dawsonite-type hydroxymetalocarbonate precursor compounds for catalytic Ho, Sm, and La oxides

Chemical interactions in mixed, aqueous solutions of NH₄HCO₃ and M(NO₃)₃·9H₂O, where M stands for Ho, Sm, or La, were facilitated under various hydrothermal treatment conditions (pH 8-12 and temperature = 75-135 °C). The solution chemistry established did not make available necessary concentrations of soluble HCO₃⁻ and MO(OH)₂⁻ species for the formation of dawsonite-type ammonium hydroxymetalocarbonates, NH₄M(CO₃)(OH)₂, but, alternatively, high concentrations of soluble CO₃²⁻, and M(H₂O)_n³⁺ or M(H₂O)_n−1(OH)²⁺ facilitating, respectively, precipitation of corresponding hydrated carbonate, M₂(CO₃)₂·2H₂O, or carbonate hydroxide, MCO₃(OH). X-ray powder diffractometry, infrared spectroscopy, and thermal analyses proved alternative formation of Ho₂(CO₃)₃·2H₂O or LaCO₃(OH) under the whole set of hydrothermal treatment conditions probed, and Sm₂(CO₃)₃·2H₂O at pH < 10 or SmCO₃(OH) at pH ≥ 10, thus implying dependence of the composition of the product carbonate compound on the hydrolysability of the initial M(H₂O)_n³⁺ species and, hence, the metal ionic size (La > Sm > Ho). Calcination of the various hydrothermal treatment products at ≥600 °C resulted in the thermal genesis of the corresponding sesqui-oxides (M₂O₃). Bulk and surface characterization studies of the product oxides, employing N₂ sorptiometry and scanning electron microscopy, in addition to the above analytical techniques, revealed overall strong crystallinity, large average crystallite size, and well-defined particle morphology. They revealed, moreover, surfaces, though of limited accessibilities (≤13 m²/g), exposing OH groups of various coordination symmetries and, hence, acid-base properties, thus furnishing promising surface catalytic attributes.     

Ion exchange and electrochemical evaluation of the microporous phosphate Li9Fe7(PO4)10

A new lithium iron(III) phosphate, Li₉Fe₇(PO₄)₁₀, has been synthesized and is currently under electrochemical evaluation as an anode material for rechargeable lithium-ion battery applications. The sample was prepared via the ion exchange reaction of Cs₅K₄Fe₇(PO₄)₁₀1 in the 1 M LiNO₃ solution under hydrothermal conditions at 200 °C. The fully Li⁺-exchanged sample Li₉Fe₇(PO₄)₁₀2 cannot yet be synthesized by conventional high-temperature, solid-state methods. The parent compound 1 is a member of the Cs_9−xK_xFe₇(PO₄)₁₀ series that was previously isolated from a high-temperature (750 °C) reaction employing the eutectic CsCl/KCl molten salt. The polycrystalline solid 1 was first prepared in a stoichiometric reaction via conventional solid-state method then followed by ion exchange giving rise to 2. Both compounds adopt three-dimensional structures that consist of orthogonally interconnected channels where electropositive ions reside. It has been demonstrated that the Cs_9−xK_xFe₇(PO₄)₁₀ series possesses versatile ion exchange capabilities with all the monovalent alkali metal and silver cations due to its facile pathways for ion transport. 1 and 2 were subject to electrochemical analysis and preliminary results suggest that the latter can be considered as an anode material. Electrochemical results indicate that Li₉Fe₇(PO₄)₁₀ is reduced below 1 V (vs. Li) to most likely form a Fe(0)/Li₃PO₄ composite material, which can subsequently be cycled reversibly at relatively low potential. An initial capacity of 250 mAh/g was measured, which is equivalent to the insertion of thirteen Li atoms per Li_9+xFe₇(PO₄)₁₀ (x = 13) during the charge/discharge process (Fe²⁺ + 2e → Fe⁰). Furthermore, 2 shows a lower reduction potential (0.9 V), by approximately 200 mV, and much better electrochemical reversibility than iron(III) phosphate, FePO₄, highlighting the value of improving the ionic conductivity of the sample.     

Effect of dispersant on preparation of barium-strontium titanate powders through oxalate co-precipitation method

The quantitative precipitation of barium-strontium titanyl oxalate: (Ba_0.6Sr_0.4TiO(C₂O₄)₂·4H₂O, BSTO) precursor powders were successfully prepared through oxalate co-precipitation method. The pyrolysis of BSTO at 800 °C/4 h produced the barium-strontium titanate (Ba_0.6Sr_0.4TiO₃, BST) powders. Two kinds of dispersants namely ammonium salt of poly mathacrylic acid (PMAA-NH₄) and polyethylene glycol (PEG) were added respectively during the co-precipitation procedure. The powders were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM), etc. Experimental results show that the addition of the dispersants reduced the productive rate of BST powders. The BSTO and BST powders obtained by aforementioned technique without dispersants were homogeneous with quasi-orbicular morphology. The particles grew into spindle shape with the effect of PEG. The morphology homogeneity was broke with small grains as well as large agglomerated particles concurrent when PMAA-NH₄ was added. The mechanism of the effect of the two dispersants was investigated in detail.     

Low temperature synthesis of nanocrystalline Li4Mn5O12 by a hydrothermal method

A mild hydrothermal method using Li-birnessite (Li_xMnO₂·nH₂O) ultrafine fiber as the precursor has been adopted to prepare Li₄Mn₅O₁₂, which is of interest as an electrode material for 3 V rechargeable lithium ion batteries. X-ray diffraction data reveal that the obtained powders have a pure spinel structure with a lattice constant of 8.135 Å. The scanning electron microscopy image of the obtained powders shows the particles are cubic-shaped whose average size is about 40-50 nm. The results from inductively coupled plasma-atomic emission spectroscope and wet chemical analysis indicate that a Li/Mn ratio of 0.796, and an average valence of 3.96 of Mn ion have been achieved in the as-prepared products. The thermogravimetric and differential thermal analysis data also agree with the previous reports on Li₄Mn₅O₁₂, suggesting that near stoichiometry of Li₄Mn₅O₁₂ has been synthesized by this procedure at the rather low temperature 110°C.     

Hydrothermal preparation of PbS crystals and shape evolution

In the current paper, we successfully prepared lead sulfide (PbS) microcrystals with various shapes in a simple aqueous system using the hydrothermal synthesis route. Experimental results indicated that the change of the molar ratio of Pb²⁺/S₂O₃²⁻ could significantly influence the morphology of the product while keeping the other experimental conditions constant: with the decrease of the molar ratio of Pb²⁺/S₂O₃²⁻ from 1:1 to 1:4, the shape of the products varied from tri-prism, cube to magic-square structure. Changing the reaction temperature had big effect on the shape of the product: flower-shaped product was obtained at 80 °C and cube-shaped products were produced at 120 °C. When the reaction time varied, the shapes of the as-obtained PbS crystals also changed. At the same time, SEM observations showed that the counter-anions for Pb²⁺ could influence the shape of the product: Pb(NO₃)₂ being used as lead ion sources, most flower-shaped and few cubic PbS crystals were produced; while PbSO₄ as lead ion source, the PbS cubes were obtained. An evolution process was described based on experimental facts.     

Preparation and visible-light activity of silver vanadate for the degradation of pollutants

Monoclinic structure silver vanadate Ag₃VO₄ was prepared by hydrothermal process. The effects of the ratio of silver to vanadium in starting material, hydrothermal temperature on surface morphologies, structure and photoactivity of Ag₃VO₄ for the decolorization azodye acid red B under visible irradiation were investigated. The Ag₃VO₄ prepared in the excess vanadium at 160 °C for 48 h exhibited highest visible-light-driven activity. Excess vanadium in the preparation increased the crystallinity and suppressed the formation of grain boundaries, while the formation of Ag⁰ on the surface of the catalyst promoting the electron-hole separation and interfacial charge transfer, resulting in an increase in the photocatalytic activity. Furthermore, the activity of the Ag₃VO₄ was increased by 11 times when NiO was loaded, which also shows high activities for the decomposition of phenol and aniline. It is possible due to the formation of a short-circuited microphotoelectrochemical cell enhancing the separation of photogenerated electron-hole pairs.     

Hydrothermal synthesis, characterization, and influence factors of PbTe nanocrystals

In the present paper, we successfully prepared PbTe nanocrystals in a simple aqueous system via the hydrothermal route employing PbO, Te powders and N₂H₄·H₂O as the starting reactants at 150 °C for 14 h. Some factors affecting the morphologies of the PbTe nanocrystals, such as the reaction temperature, time, the amount of NaOH, sorts of reductants and Pb²⁺ ion sources, were systematically investigated. Experimental results indicated that, under keeping the other experimental conditions constant: raising the reaction temperature, the shapes of the as-obtained PbTe hardly changed, while decreasing the temperature, some PbTe dendrites were obtained; the short reaction time availed to obtain cubes with a hole in the center of each face; more amounts of NaOH were favorable to the formation of regular PbTe nanocuboids. When NaBH₄ was used as the reductant, a large amount of near spherical PbTe nanocrystals was produced; while NaH₂PO₂ was used, many PbTe crystals with hollow framework structures were obtained. When Pb(CH₃COO)₂ was used as the Pb²⁺ ion source, some dendrites made of many irregular particles were generated; while PbSO₄ was employed, many PbTe nanocuboids were produced. A possible formation mechanism of PbTe nanocrystals was proposed based on the experimental results.     

Preparation of bismuth oxyiodides and oxides and their photooxidation characteristic under visible/UV light irradiation

Bismuth oxyiodides and oxides were prepared by a solution combination with thermal treatment method. The prepared samples were characterized by X-ray diffraction, thermogravimetry, scanning electron microscopy, transmission electron microscopy, and UV-vis diffuse reflectance spectra, and Brunauer-Emmett-Teller surface areas. The photooxidation activity of the samples was evaluated by photocatalytic decolorization of acid orange II under both visible light (λ > 420 nm) and UV light (λ = 365 nm) irradiation. Results show that a series of changes in the compounds take place during the course of calcination, described as: BiOI → Bi₅O₇I → α-Bi₂O₃. Under visible light irradiation, the photocatalytic activities follow the order: BiOI > Bi₅O₇I > Bi₅O₇I/Bi₂O₃ mixture > Bi₂O₃, which is mainly attributed to the different absorption ability to visible light due to the different band gap energy; the activities are in the order: BiOI < Bi₂O₃ < Bi₅O₇I/Bi₂O₃ mixture < Bi₅O₇I under UV light irradiation, which is mainly caused by the different oxidability.     

Low temperature growth of single crystalline germanium nanowires

Ge nanowires have been prepared at a low temperature by a simple hydrothermal deposition process using Ge and GeO₂ powders as the starting materials. These as-prepared Ge nanowires are single crystalline with the diameter ranging from 150 nm to 600 nm and length of several dozens of micrometers. The photoluminescence spectrum under excitation at 330 nm shows a strong blue light emission at 441 nm. The results of the pressure and GeO₂ content dependences on the formation and growth of Ge nanowires show that the hydrothermal pressure and GeO₂ content play an essential role on the formation and growth of Ge nanowires under hydrothermal deposition conditions. The growth of Ge nanowires is proposed as a solid state growth mechanism.     

Template-free synthesis of ZnWO4 powders via hydrothermal process in a wide pH range

ZnWO₄ powders with different morphologies were fabricated through a template-free hydrothermal method at 180 °C for 8 h in a wide pH range. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-visible and luminescence spectrophotometers were applied to study the effects of pH values on crystallinity, morphology, optical and luminescence properties. The XRD results showed that the WO₃ + ZnWO₄, ZnWO₄, and ZnO phases could form after hydrothermal processing at 180 °C for 8 h with the pH values of 1, 3-11, and 13, respectively. The SEM and TEM observation revealed that the morphological transformation of ZnWO₄ powders occurred with an increase in pH values as follows: star anise-, peony-, and desert rose-like microstructures and soya bean- and rod-like nanostructures. The highest luminescence intensity was found to be in sample consisting of star anise-like crystallites among all the samples due to the presence of larger particles with high crystallinity resulted from the favorable pH under the current hydrothermal conditions.     

Synthesis of FePO4 cathode material for lithium ion batteries by a sonochemical method

Hydrated amorphous FePO₄ was synthesized by a sonochemical reaction method, in which a solution of (NH₄)₂HPO₄ and FeSO₄·7H₂O was irradiated by an ultrasonic wave. From this material, two kinds of cathode materials were easily prepared: (1) an amorphous sample prepared by heating at 350 °C and (2) a crystalline sample prepared by heating at 700 °C. Both samples consisted of homogeneous sub-micron particles. The amorphous sample of FePO₄ exhibited high discharge capacities with more than 100 mAh g⁻¹ in the range of 3.9-2.0 V versus Li/Li⁺ at a current rate of 0.2 C. The sonochemical synthesis proposed herein has the following advantages: no use of oxidation agents for production of trivalent iron ions, reduction in reaction time, control of particle size, and enlargement in surface area for the preparation of the cathode material.     

Thermal stability against reduction of LaMn1−yCoyO3 perovskites

Thermal and reduction-oxidation stability of substituted LaMn_1−yCo_yO₃ perovskite-type oxides (0.0 ≤ y_Co ≤ 1.0) prepared by the citrate route have been studied by means of surface area, X-ray diffraction, FTIR spectroscopy and magnetic properties. The perovskite orthorhombic structure is found for y_Co ≤ 0.5, with the exception of y_Co = 0.1, which corresponds better to rhombohedral LaMnO_3.15. For y_Co > 0.5 the diffraction profiles are quite similar to the cobaltite’s rhombohedral structure. Magnetic iso-field studies (ZFC-FC) reveal that, for y_Co ≤ 0.50, the system presents an antiferromagnetic canted-like ordering of the Mn/Co sublattice, in which the presence of divalent Co ion creates Mn³⁺-Mn⁴⁺ pairs that interact ferromagnetically through the oxygen orbital. This interpretation is confirmed by the magnetization loops, in which the magnetic moment increases when substituting Mn for Co. Therefore, the general trend is: for y_Co ≤ 0.5, the Co ions are inserted in the manganite structure and for y_Co > 0.5, the Mn ions are inserted in cobaltite structure. The enhancement of the ferromagnetic properties and the thermal stability against reduction for y_Co = 0.5 is attributed to optimized Co²⁺-Mn⁴⁺ interactions.     

δ-Phase to defect fluorite (order-disorder) transition in the R2O3-MO2 (R = Sc, Tm, Lu; M = Zr, Hf) systems

We have studied the δ-phase to defect fluorite F* (order-disorder) transition in the R₄M₃O₁₂ (R = Sc, Tm, Lu; M = Zr, Hf) compounds. The temperature of the δ-F* phase transition in Tm₄Zr₃O₁₂ is ∼1600 °C. The rate of this transition in R₄Zr₃O₁₂ (R = Sc, Tm, Lu) decreases markedly with decreasing difference in ionic radius between the R³⁺ and Zr⁴⁺, leading to stabilization of the δ-phases R₄Zr₃O₁₂ with R = Sc and Lu at high temperatures (∼1600 °C). During slow cooling (5 °C/h), the high-temperature defect fluorites F*-R₂Hf₂O₇ (R = Tm, Lu) decompose reversibly to form the δ-phases R₄Hf₃O₁₂. Some of the materials studied exhibit microdomains formation effects, typical of the fluorite-related oxide compounds in the R₂O₃-MO₂ (M = Ti, Zr, Hf) systems of the heavy rare earths. The high-temperature defect fluorites F*-R₄M₃O₁₂ (R = Tm, Lu; M = Zr, Hf) as a rule contain antiphase microdomains of δ-R₄Zr₃O₁₂. After slow cooling (5 °C/h), such microdomains are large enough for the δ-phase to be detected by X-ray diffraction. The conductivity data for R₄M₃O₁₂ (R = Sc, Tm, Lu; M = Zr, Hf) and Ln₂Hf₂O₇ (Ln = Dy, Lu) prepared by different procedures show that the rhombohedral phases δ-R₄M₃O₁₂ (R = Sc, Tm, Lu; M = Zr, Hf) are poorer conductors than the defect fluorites, with 740 °C conductivity from 10⁻⁶ to 10⁻⁵ S/cm. The conductivity drops with decreasing rare-earth ionic radius and, judging from the E_a values obtained (1.04-1.37 eV), is dominated by oxygen ion transport. The highest conductivity, ∼6 × 10⁻⁴ S/cm at 740 °C, is offered by the rapidly cooled F*-Dy₂Hf₂O₇. In the fluorite homologous series, oxygen ion conductivity decreases in the order defect pyrochlore > defect fluorite > δ-phase.     

Preparation and hydrothermal annealing of pure metastable β-MnS thin films by chemical bath deposition (CBD)

Pure metastable β-MnS thin films have been deposited by chemical bath deposition (CBD) method and subsequently annealed in a Na₂S solution (denoted as hydrothermal annealing). The effects of preparative parameters and hydrothermal annealing on structure, morphology and optical property of the films have been investigated. Experimental results indicate that the crystalline β-MnS thin films can be prepared at a low concentration of Mn and S ions without using any organic chelator. The as-deposited β-MnS can be transformed to γ-phase MnS after the hydrothermal treatment in an autoclave at 200 °C for 1 h. The estimated E_g values are in the range of 3.15-3.18 eV.     

Crystal structure, thermal analysis and IR spectrometric investigation of bis(o-anisidinium) sulfate (C7H10NO)2SO4

Chemical preparation, X-ray single-crystal, thermal behaviour, and IR spectroscopy investigations are given for a new organic cation sulfate (C₇H₁₀NO)₂SO₄ (denoted BOAS) in the solid state. This compound crystallizes in the monoclinic space group P2₁/c. The unit cell dimensions are: a = 7.010(3) Å, b = 11.142(5) Å, c = 20.770(8) Å, β = 95.27(3)° with V = 1615.4(12) Å³ and Z = 4. The structure has been solved using a direct method and refined to a reliability R factor of 0.047. The title compound consists of a framework of isolated SO₄ tetrahedral interleaved with organic molecules, so as to build isolated ribbons parallel to a-axis. In the present work, we describe the crystal structure, thermal behaviour and IR analysis of this new compound.     

Crystal structure and physicochemical properties of a new organic condensed phosphate (C7H10NO)3P3O9·4H2O

Chemical preparation, X-ray characterization, IR spectroscopy and thermal analysis of a new cyclotriphosphate: (C₇H₁₀NO)₃P₃O₉·4H₂O abbreviated as OACTP, are reported. This mixed organo-mineral compound crystallizes in the monoclinic system with P2₁/n space group, the unit cell dimensions are: a = 6.605(3) Å, b = 26.166(3) Å, c = 18.671(8) Å, β = 91.95(3)°, Z = 4 and V = 3255(2) Å³. The structure was solved using a direct method and refined to a reliability R-factor of 0.043 using 3931 independent reflections (I > 2σI). Atomic arrangement exhibits infinite (P₃O₉·2H₂O)_n³ⁿ⁻ chains connected by organic cations. The thermal behavior and the IR spectroscopic studies of this new compound are discussed.