Hydrothermal synthesis of WO3·1/3H2O nanorods and study of their electrical properties

Crystalline tungsten oxide hydrate (WO₃·1/3H₂O) nanorods have been prepared by a hydrothermal process using Na₂WO₄·2H₂O and 4-phenylbutylamine as a structure-directing agent. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray analysis (EDX), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy and thermal analysis techniques have been used to characterize the structure, morphology and composition of the nanorods. The WO₃·1/3H₂O nanorods are up to several hundred nanometers in length, and the widths and thicknesses are 40 and 8 nm, respectively. A study of the electric properties in the temperature range 170–730 °C and frequency range 5–13 MHz is reported. The obtained results show that the activation energies are about 0.07, 0.63 and 2.46 eV for o-WO₃·1/3H₂O, h-WO₃ and m-WO₃, respectively. The as-synthesized materials are promising for chemical and energy-related applications such as catalysts and electrochemical devices, and may be applied in rechargeable lithium-ion batteries.     

Homogeneous one-dimensional structured Tb(OH)3:Eu nanorods: Hydrothermal synthesis, energy transfer, and tunable luminescence properties

Nearly monodisperse, homogeneous and well-defined one-dimensional Tb_(1−x)(OH)₃:xEu³⁺ (x=0-3 mol%) nanorods have been prepared through hydrothermal method. The size of the Tb(OH)₃:Eu³⁺ rods could be modulated from nano- to micro-scale by using different amount of ammonia solution. They present highly crystallinity in spite of the moderate reaction temperature. Under ultraviolet excitation into the f→f transition of Tb³⁺ at 382 nm, Tb(OH)₃ samples show the characteristic emission of Tb³⁺ corresponding to ⁵D₄→⁷F_{6, 5, 4, 3} transitions; whereas Tb(OH)₃:Eu³⁺ samples mainly exhibit the characteristic emission of Eu³⁺ corresponding to ⁵D₀→⁷F_{1, 2, 4} transitions due to an efficient energy transfer occurs from Tb³⁺ to Eu³⁺. The increase of Eu³⁺ concentration leads to the increase of the energy transfer efficiency from Tb³⁺ to Eu³⁺. The PL colors of Tb(OH)₃:xEu³⁺ phosphors can be easily tuned from green, yellow, orange, to red by changing the doping concentration (x) of Eu³⁺.     

Preparation and characterization of gadolinium hydroxide single-crystalline nanorods by a hydrothermal process

The Gd(OH)3 nanorods with diameters of ca.40-60 nm and lengths of more than 400-550 nm have been prepared by a novelhydrothermal technique.The structural features and chemical composition of the nanorods were investigated by X-ray diffraction(XRD),transmission electron microscopy(TEM),and field emission scanning electron microscope(FESEM),selected areaelectron diffraction(SAED),and high resolution transmission electron microscopy(HRTEM).The possible mechanism for theformation of Gd(OH)3 nanorods was proposed.     

Formation of α-Mn2O3 nanorods via a hydrothermal-assisted cleavage-decomposition mechanism

A hydrothermal cleavage-decomposition mechanism was used to synthesize single-crystal α-Mn₂O₃ nanorods at 160 °C for 16 h using KMnO₄ as manganese source and CTAB as reducing regent. The as-synthesized products were characterized by powder X-ray diffraction, transmission electron microscopy, high-resolution transmission electron microscopy and infrared spectrum. The results indicate that the reaction temperature is a crucial factor for the formation of α-Mn₂O₃ nanorods. These nanorods exhibit single-crystal nature, and have an average diameter of 36 nm and lengths of up to 1 μm. Based on our experimental results, a hydrothermal cleavage-decomposition mechanism has been proposed on the formation of α-Mn₂O₃ nanorods.     

A simple method to prepare ZnO and Al(OH)3 nanorods by the reaction of the metals with liquid water

Reaction of liquid water with Zn and Al powders and foils have been investigated in the 25-75 °C range. The reaction of Zn metal powder with water in this temperature range yields ZnO nanorods. The diameter of the nanorods decreases slightly with the increase in the reaction temperature, accompanied by an increase in the relative intensity of UV emission band. Zn metal foils also yield ZnO nanorods on reaction with water in the 25-75 °C range. Reaction of Al metal powder or foil with water in the 25-75 °C range yields Al(OH)₃ nanorods. The formation of ZnO and Al(OH)₃ nanorods by the reaction of the metals with water is suggested to occur because of the decomposition of water by the metal giving hydrogen.     

Hydrothermal synthesis of two perovskite rare-earth manganites, HoMnO3 and DyMnO3

Two perovskite rare-earth manganites RMnO₃ (R=Ho, Dy) were synthesized from the hydrothermal redox reactions of KMnO₄ and MnCl₂ at 250 °C and characterized by means of X-ray diffraction, scanning electron microscopy and SQUID. They are orthorhombic, whereas the hexagonal phases, which were competitive strongly with the orthorhombic phases in solid-state reactions, are avoided in the hydrothermal systems. The pure metastable manganites may serve as a model for understanding the magnetisms of Jahn-Teller distortion and charge ordering. This new synthetic approach leaves many rooms for new doped or undoped RMnO₃ compounds.     

Syntheses and structures of three new scandium selenites: Sc2(SeO3)3·H2O, Sc2 (SeO3)3·3H2O and CsSc3(SeO3)4 (HSeO3)2·2H2O

Three new hydrated scandium selenites have been hydrothermally synthesized as single crystals and structurally and physically characterized. Sc₂(SeO₃)₃·H₂O crystallizes as a new structure type containing novel ScO₇ pentagonal bipyramidal and ScO₆₊₁ capped octahedral coordination polyhedra. Sc₂(SeO₃)₃·3H₂O contains typical ScO₆ octahedra and is isostructural with its M₂(SeO₃)₃·3H₂O (M=Al, Cr, Fe, Ga) congeners. CsSc₃(SeO₃)₄(HSeO₃)₂·2H₂O contains near-regular ScO₆ octahedra and has essentially the same structure as its indium-containing analogue. All three phases contain the expected pyramidal [SeO₃]^2- selenite groups. Crystal data: Sc₂(SeO₃)₃·3H₂O, M_r=524.85, trigonal, R3c (No. 161), , , , Z=6, R(F)=0.018, wR(F²)=0.036; Sc₂(SeO₃)₃·H₂O, M_r=488.82, orthorhombic, P2₁2₁2₁ (No. 19), , , , , Z=4, R(F)=0.051, wR(F²)=0.086; CsSc₃(SeO₃)₄(HSeO₃)₂·2H₂O, M_r=1067.60, orthorhombic, Pnma (No. 62), , , , , Z=4, R(F)=0.035, wR(F²)=0.070.     

Hydrothermal synthesis and crystal structure of a layered vanadium oxide with an interlayer metal coordination complex: [Co(phen)3][V10O26]·H2O

A novel compound, [Co(phen)₃][V₁₀O₂₆]·H₂O, was hydrothermally synthesized and characterized by single-crystal X-ray diffraction. This compound crystallizes in the orthorhombic space group Ccca with a=13.447(3), b=29.936(6), c=23.252(5) Å, V=9360(3) Å³, Z=8 and R=0.0285. Data were collected on a Rigaku R-AXIS RAPID IP diffractometer at 293 K in the range of 1.36<θ<24.99°. The structure of the compound consists of vanadium oxide layers, which are built up from the infinite VO₄ chains by corners and edges sharing. The [Co(phen)₃]²⁺ complexes occupy the interlayer space and contact each other via π−π stacking interactions of the phen groups to form infinite one-dimensional chains.     

WO3/TiO2 catalysts: Morphological and structural properties

Titania-supported tungsten oxide catalysts with different W loadings up to 9 wt. % and calcined at different temperatures have been prepared and characterized. It is found that W hinders the initial sintering of anatase, providing thermal stability. The interaction of W with TiO₂ and the amount of hydroxy groups present on the surface can limit diffusion, thus reducing the sintering rate.     

New one-dimensional uranyl and neptunyl iodates: crystal structures of K3[(UO2)2(IO3)6](IO3)·H2O and K[NpO2(IO3)3]·1.5H2O

The uranyl and neptunyl(VI) iodates, K₃[(UO₂)₂(IO₃)₆](IO₃)·H₂O (1) and K[NpO₂(IO₃)₃]·1.5H₂O (2), have been prepared and crystallized under mild hydrothermal conditions. The structures of 1 and 2 both contain one-dimensional _∞¹[AnO₂(IO₃)₃]¹⁻(An=U,Np) ribbons that consist of approximately linear actinyl(VI) cations bound by iodate anions to yield AnO₇ pentagonal bipyramids. The AnO₇ units are linked by bridging iodate anions to yield chains that are in turn coupled by additional iodate anions to yield ribbons. The edges of the ribbons are terminated by monodentate iodate anions. For 1 and 2, K⁺ cations and water molecules separate the ribbons from one another. In addition, isolated iodate anions are also found between _∞¹[UO₂(IO₃)₃]¹⁻ ribbons in 1. In order to aid in the assignment of oxidation states in neptunyl containing compounds, a bond-valence sum parameter of 2.018 Å for Np(VI) bound exclusively to oxygen has been developed with b=0.37 Å. Crystallographic data (193 K, MoKα, λ=0.71073): 1, triclinic, , a=7.0609(4) Å, b=14.5686(8)  Å, c=14.7047(8)  Å, α=119.547(1)°, β=95.256(1)°, γ=93.206(1)°, Z=2, R(F)=2.49% for 353 parameters with 6414 reflections with I>2σ(I); (203 K, MoKα, λ=0.71073): 2, monoclinic, P2₁/c, a=7.796(4)  Å, b=7.151(3)  Å, c=21.79(1)  Å, β=97.399(7)°, Z=4, R(F)=6.33% for 183 parameters with 2451 reflections with I>2σ(I).     

[NH3CH2CHCH3NH3]][B8O11(OH)4]·H2O: Synthesis and characterization of the first 1D borate templated by 1,2-diaminopropane

A new hydrated borate compound, [NH₃CH₂CHCH₃NH₃]][B₈O₁₁(OH)₄]·H₂O 1, has been synthesized in the presence of 1,2-diaminopropane acting as a structure-directing agent under mild conditions. Its structure was determined by single crystal X-ray diffraction and further characterized FTIR, elemental analysis, powder X-ray diffraction and thermogravimetric analysis. Compound 1 crystallizes in the monoclinic system, space group P2₁/c (No. 14), a=10.0787(7) Å, b=8.8482(6) Å, c=19.3097(4) Å, β=91.352(6)°, V=1721.53(2) Å³, and Z=4. The structure consists of infinite open-branched borate chains constructed from [B₃O₆(OH)] units, onto which the [B₅O₇(OH)₃] groups are grafted. It represents the first example of one-dimensional borate templated by an organic amine. The adjacent borate chains are further linked together by extensive hydrogen bonds to form a 3D supramolecular network. The diprotonated organic amines and guest water molecules are filled in the free space of the hydrogen-bonded network and interact with the inorganic framework by extensive hydrogen bonds.     

Two new octahedral/pyramidal frameworks containing both cation channels and lone-pair channels: syntheses and structures of Ba2MnMn2(SeO3)6 and PbFe2(SeO3)4

The hydrothermal syntheses, single crystal structures, and some properties of Ba₂Mn^IIMn₂^III(SeO₃)₆ and PbFe₂(SeO₃)₄ are reported. These related phases contain three-dimensional frameworks of vertex (FeO₆) and vertex/edge linked (MnO₆) octahedra and SeO₃ pyramids. In each case, the MO₆/SeO₃ framework encloses two types of 8 ring channels, one of which encapsulates the extra-framework cations and one of which provides space for the Se^IV lone pairs. Crystal data: Ba₂Mn₃(SeO₃)₆, M_r=1201.22, monoclinic, P2₁/c (No. 14), a=5.4717 (3) Å, b=9.0636 (4) Å, c=17.6586 (9) Å, β=94.519 (1)°, V=873.03 (8) Å³, Z=2, R(F)=0.031, wR(F²)=0.070; PbFe₂(SeO₃)₄, M_r=826.73, triclinic, (No. 2), a=5.2318 (5) Å, b=6.7925 (6) Å, c=7.6445 (7) Å, α=94.300 (2)°, β=90.613 (2)°, γ=95.224 (2)°, V=269.73 (4) Å³, Z=1, R(F)=0.051, wR(F²)=0.131.     

Synthesis and photoluminescence of single crystals europium ion-doped BaF2 cubic nanorods

In this work, we used the hydrothermal method to synthesize Eu³⁺ ion-doped cubic BaF₂ nanorods, which is a luminescent material. The clubbed structures were well crystallized and exhibited face-centred cubic structures, as indicated by powder X-ray diffraction, scanning electron microscopy, electron diffraction, and transmission electron microscopy. The luminescent properties were studied, and local symmetry surrounding Eu³⁺ ions and electronic transition processes included. The results indicated that Eu³⁺ occupied only one C_4ν site in nanorods.     

Microemulsion-mediated hydrothermal synthesis and characterization of zircon-type LaVO4 nanowires

The zircon-type tetragonal (t-) LaVO₄ nanowires were controlled synthesized by a new approach, a microemulsion-mediated hydrothermal method, in which the aqueous cores of sodium dodecyl sulfate (SDS)/cyclohexane/n-hexanol/water microemulsion were used as constrained microreactors for a controlled growth of t-LaVO₄ nanocrystals under hydrothermal conditions. The microemulsion exists stably just at room temperature and not under hydrothermal conditions, in addition, the as-obtained nanowires are much larger than the microemulsion droplets, so that the microemulsion does not simply act as a template, but rather directs crystal growth into nanowires presumably by interacting with the surface of the growing crystal. A series of experimental results indicated that several experimental parameters, such as the SDS concentration, the species and content of the cosurfactant play important roles in the morphological control of the t-LaVO₄ nanocrystals. Possible formation mechanism of t-LaVO₄ nanowires is also discussed.     

ZnO porous structures synthesized by CTAB-assisted hydrothermal process

ZnO porous structures have been fabricated by cetyltrimethylammonium bromide (CTAB)-assisted hydrothermal process. X-ray diffraction (XRD) pattern indicated that the synthesized ZnO porous structures were hexagonal. It is found that CTAB influences the morphology of ZnO structures. On the basis of structural information provided by XRD, SEM, and TEM, a growth mechanism is proposed for the formation of ZnO porous structures.     

Hydrothermal synthesis and characterization of a new 3D vanadium(III) phosphite (C4H8N2H4)0.5(C4H8N2H3)[V4(HPO3)7(H2O)3]1.5H2O

A new vanadium(III) phosphite, (C₄H₈N₂H₄)_0.5(C₄H₈N₂H₃)[V₄(HPO₃)₇(H₂O)₃]1.5H₂O, has been synthesized hydrothermally by using V₂O₅, H₃PO₃ as reactants, piperazine as the structure-directing agent. The as-synthesized product was characterized by powder X-ray diffraction, IR spectroscopy, inductively coupled plasma analysis, thermogravimetric analysis, and SQUID magnetometer. Single-crystal X-ray diffraction analysis shows that the title compound crystallized in the trigonal space group (No. 165) with the parameters: , , and Z=4. Its structure is built up by alternation of octahedral VO₆ or VO₅(H₂O) and pseudo-pyramidal HPO₃ units to form infinite 2D layers, and these layers are interconnected by sharing vertex-oxygen with octahedral VO₆ units to generate a 3D open-framework structure with 12-membered ring channels in a and b directions, respectively, where there exist entrapped diprotonated and mono-protonated piperazine cations, and water molecules. Magnetic measurement indicates that paramagnetic behavior is observed down to 4 K.     

Syntheses, structures, and properties of Ag4(Mo2O5)(SeO4)2(SeO3) and Ag2(MoO3)3SeO3

Ag₄(Mo₂O₅)(SeO₄)₂(SeO₃) has been synthesized by reacting AgNO₃, MoO₃, and selenic acid under mild hydrothermal conditions. The structure of this compound consists of cis-MoO₂²⁺ molybdenyl units that are bridged to neighboring molybdenyl moieties by selenate anions and by a bridging oxo anion. These dimeric units are joined by selenite anions to yield zigzag one-dimensional chains that extended down the c-axis. Individual chains are polar with the C₂ distortion of the Mo(VI) octahedra aligning on one side of each chain. However, the overall structure is centrosymmetric because neighboring chains have opposite alignment of the C₂ distortion. Upon heating Ag₄(Mo₂O₅)(SeO₄)₂(SeO₃) looses SeO₂ in two distinct steps to yield Ag₂MoO₄. Crystallographic data: (193 K; MoKα, λ=0.71073 Å): orthorhombic, space group Pbcm, a=5.6557(3), b=15.8904(7), c=15.7938(7) Å, V=1419.41(12), Z=4, R(F)=2.72% for 121 parameters with 1829 reflections with I>2σ(I). Ag₂(MoO₃)₃SeO₃ was synthesized by reacting AgNO₃ with MoO₃, SeO₂, and HF under hydrothermal conditions. The structure of Ag₂(MoO₃)₃SeO₃ consists of three crystallographically unique Mo(VI) centers that are in 2+2+2 coordination environments with two long, two intermediate, and two short bonds. These MoO₆ units are connected to form a molybdenyl ribbon that extends along the c-axis. These ribbons are further connected together through tridentate selenite anions to form two-dimensional layers in the [bc] plane. Crystallographic data: (193 K; MoKα, λ=0.71073 Å): monoclinic, space group P2₁/n, a=7.7034(5), b=11.1485(8), c=12.7500(9) Å, β=105.018(1) V=1002.7(2), Z=4, R(F)=3.45% for 164 parameters with 2454 reflections with I>2σ(I). Ag₂(MoO₃)₃SeO₃ decomposes to Ag₂Mo₃O₁₀ on heating above 550 °C.     

Mild hydrothermal synthesis and ferrimagnetism of Pr3Fe5O12 and Nd3Fe5O12 garnets

Two pure light rare earth iron garnets Pr₃Fe₅O₁₂ and Nd₃Fe₅O₁₂ single crystals were synthesized under mild hydrothermal conditions and structurally characterized by single crystal and powder X-ray diffraction methods. Both compounds crystallize in cubic space group Ia3?d with lattice parameters a=12.670(2) Å for Pr₃Fe₅O₁₂ and a=12.633(2) Å for Nd₃Fe₅O₁₂, respectively. The synthesis of compounds was studied with regard to phase evolution and morphology development with hydrothermal conditions. We proposed the formation mechanisms and formulated a reasonable explanation for their growth habits. Ferrimagnetic Curie temperatures which have been inferred from thermo-magnetization curves were 580 K for Pr₃Fe₅O₁₂ and 565 K for Nd₃Fe₅O₁₂, and the transitions of long range order were also evidenced by differential scanning calorimetry method. The result of magnetic properties has shown that moments of the large radius Pr³⁺ and Nd³⁺ ions are parallelly coupled with net moments of iron ions.     

Enhanced visible-light absorption and dopant distribution of iodine-TiO2 nanoparticles synthesized by a new facile two-step hydrothermal method

In order to prepare visible-light responsive iodine-doped TiO₂, a new facile synthetic approach was proposed, which started with the cost-efficient and environmentally friendly precursor of undoped anatase TiO₂ to form nanotube structures as templates that collapsed and recrystallized into I-TiO₂ nanopowders in HIO₃ solution, followed by annealing at different temperatures. The modification of TiO₂ to incorporate iodine and form titanium dioxide with significantly enhanced absorption in the visible range of the spectrum was investigated. The extent of iodine dopant incorporation was determined by X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray analysis (EDX) and was found to be homogenously distributed on each nanostructure as determined by electron energy-loss spectroscopy (EELS) elemental mapping and EDX spectroscopy. The modified TiO₂ exhibits a dramatically extended absorption edge beyond 800 nm as compared to the original and unmodified TiO₂.     

Controlling the morphology of yttrium oxide through different precursors synthesized by hydrothermal method

Y₂O₃ sheets, rods, needles and tubes were synthesized from three precursors through hydrothermal reactions followed by calcination. The phase distribution and decomposition behaviors of the three precursors, Y₂(OH)_5.14(NO₃)_0.86·H₂O, Y₄O(OH)₉(NO₃) and hexagonal Y(OH)₃, were investigated. The reaction temperature and initial pH value during the hydrothermal reaction showed great influence on the shape and particle size of the products. The precursors were converted to Y₂O₃ particles with the retained original morphology of the precursors.