Large-scale synthesis and characterization of fan-shaped rutile TiO2 nanostructures

Large-scale fan-shaped rutile TiO₂ nanostructures have been synthesized by means of a simple hydrothermal method using only TiCl₄ as titanium source and chloroform/water as solvents. The physicochemical features of the fan-shaped TiO₂ nanostructures are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected-area electron diffraction (SAED), nitrogen absorption-desorption, diffuse reflectance ultraviolet-visible spectroscopy (UV-vis) and Fourier transform infrared spectroscopy (FTIR). Structural characterization indicates that the fan-shaped TiO₂ nanostructures are composed of several TiO₂ nanorods with diameters of about 5 nm and lengths of 300-350 nm. The average pore size and BET surface area of the fan-shaped TiO₂ nanostructures are 6.2 nm and 59 m²/g, respectively. Optical adsorption investigation shows that the fan-shaped TiO₂ nanostructures possess optical band gap energy of 3.11 eV.     

Hydrothermal synthesis and characterization of LiNbO3 crystal

Lithium niobate crystal was successfully synthesized via hydrothermal synthesis method using LiOH·H₂O or LiNO₃ and Nb₂O₅ as starting materials in water or ammonia solution. X-ray diffraction (XRD), Fourier-transform infrared (FT-IR) spectra and Scanning electron microscopy (SEM) were used to characterize the as-prepared samples. The synthesis conditions such as crystallization temperature and time as well as ammonia concentration (when using LiNO₃ as Li source) were investigated. The results demonstrate that the crystallization and purity of the as-prepared samples were increased with the increase of time when temperature was at 260 °C. When using LiNO₃ as Li source a basic solution was necessary to synthesize LiNbO₃. In the present work ammonia solution was used instead of water to obtain alkalescence solvent. XRD results revealed that the as-prepared samples had a hexagonal structure. FT-IR results displayed that the LiNbO₃ phase could be completely formed and no secondary phase was found under proper conditions. SEM picture showed that the morphology of the sample was more perfect and bigger with increasing reaction time.     

Synthesis of (K, Na)NbO3 particles by high temperature mixing method under hydrothermal conditions

In order to prepare the pure (K, Na)NbO₃(KNN) particles with higher crystallinity, the high temperature mixing method (HTMM) under hydrothermal conditions was carried out in this work. The obtained samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), and high-resolution transmission electron microscopy (HRTEM). The results indicate that the KNN particles size decrease gradually with the increase of mineralization concentration in the starting solution. The ratio of K⁺/(K⁺ + Na⁺) in the starting solution has a great effect on the phase of the products, and several phases coexist in the product when the ratio of K⁺/(K⁺ + Na⁺) in the starting solution is 0.7.     

Dielectric and piezoelectric properties of alkaline-earth titanate doped (K0.5Na0.5)NbO3 ceramics

(K_0.5Na_0.5)NbO₃ (KNN) and 0.995(K_0.5Na_0.5)NbO₃-0.005AETiO₃ (AE = Mg, Ca, Sr, Ba) were successfully prepared by conventional ceramic processing and without the cold-isostatic-pressing (CIP) process. The effects of low AETiO₃ (AET) concentration on crystal structure, density, dielectric and piezoelectric properties of the KNN based ceramics were evaluated. The results show that adding MgTiO₃(MT) and BaTiO₃(BT) to KNN can lead to the appearance of a trace amount of second phase(s), reduced density and deteriorated electrical properties. Adding CaTiO₃(CT) and SrTiO₃(ST) to KNN can promote densification and optimize electrical properties. Two phase transitions at T_t-o ( the temperature at which the phase transition from orthorhombic to tetragonal occurs) and T_c (the Curie temperature) were observed in KNN and all KNN-AET ceramics, by using differential scanning calorimetry (DSC) analysis and dielectric characterization. Adding AET to KNN caused the variations of T_t-o and T_c.     

Hydrothermal preparation and characterization of TiO2:AC composites

A new photocatalyst titania:activated carbon (TiO₂:AC) composite was prepared by impregnating anatase type TiO₂ nanoparticulates onto the activated carbon surface through a mild hydrothermal route. A varied ratio of TiO₂ to AC was considered for impregnation. As-prepared TiO₂:AC composite was characterized by various techniques such as powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), BET surface area and positron annihilation lifetime spectroscopy (PALS). Powder XRD results showed the persisting nature of anatase phase of TiO₂ deposited on the activated carbon surface. The BET, FTIR and PALS results revealed the impregnation threshold. The TiO₂ particulates were well adhered and uniformly dispersed on the carbon surface as confirmed by SEM.     

(K,Na)NbO3 lead-free piezoelectric ceramics synthesized from hydrothermal powders

Among various lead-free piezoelectric materials, (K,Na)NbO₃ is a very promising candidate. In this study, (K,Na)NbO₃ ceramics were sintered from mixed KNbO₃ and NaNbO₃ powders prepared by hydrothermal reaction. These two powders were mixed with distilled water in a KNbO₃/NaNbO₃ molar ratio of 1. After sintering the mixed powder, the solid solution of (Na,K)NbO₃ ceramics was obtained. The electrical properties such as the electromechanical coupling factors k_p and k₃₃, the mechanical quality factor, Q_m, and the piezoelectric constant d₃₃ of the sintered (K,Na)NbO₃ ceramics were 0.32, 0.48, 71 (radial mode), 118 ((33)mode), and 107 pC/N, respectively.     

Hydrothermal synthesis and characterization of MoS2 nanorods

MoS₂ nanorods were successfully synthesized via hydrothermal method by adding sillicontungstic acid as an additive. The products were characterized by X-ray powder diffraction (XRD), X-ray photoelectron spectrum (XPS) and field-emission scanning electron microscopy (FESEM). XRD pattern result indicated that the as-prepared sample can be indexed to a mixture of hexagonal and rhombohedral phase MoS₂. XPS showed that the nanorods were only composed of Mo and S with atomic ratio of 1:2. FESEM images revealed that the MoS₂ rods had uniform sizes with mean diameters of about 20-50 nm and lengths of 400-500 nm. It was found that the addition of sillicontungstic acid played a crucial role in the formation of the rod-like MoS₂ in our experiment. The possible formation mechanism of MoS₂ nanorods is also discussed.     

Dielectric, ferroelectric and piezoelectric properties of Bi0.5Na0.5TiO3-(Ba0.7Ca0.3)TiO3 ceramics at morphotropic phase boundary composition

(1 − x)Bi_0.5Na_0.5TiO₃-x(Ba_0.7Ca_0.3)TiO₃ (BNT-xBCT, 0 ≤ x ≤ 0.15) solid solutions have been synthesized by a conventional solid state sintering method for obtaining a morphotropic phase boundary (MPB) with good piezoelectric properties. X-ray diffraction patterns reveal that a MPB of rhombohedral and tetragonal phases is formed at compositions 0.09 ≤ x ≤ 0.12. Addition of BCT into BNT greatly lowered coercive field E_c without degrading remanent polarization P_r. The specimen with x = 0.09 has the good piezoelectric properties: d₃₃ = 125 pC/N and k_p = 0.33. A modified Curie-Weiss law was used to fit the dielectric constant of BNT-xBCT ceramics, and a frequency dispersion was observed during the phase transitions from antiferroelectric to paraelectric in specimens with x exceeding 0.06.     

Hydrothermal growth of rutile TiO2 nanorod films on titanium substrates

Rutile TiO₂ nanorod films have been successfully prepared on titanium substrate via a hydrothermal method using Tetra-n-butyl titanate as Ti source in the presence of concentrated hydrochloric acid. The effect of Ti substrate annealing treatment and adding of additional alkali metal chlorides in hydrothermal solution on the growth of TiO₂ nanorod films has been studied using scanning electron microscopy (SEM), Raman spectroscopy, X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and water contact angle measurement. The growth mechanism of the TiO₂ nanorods on Ti substrate has also been discussed. It has shown that the initial rutile film transformed from anatase promotes the nucleation and epitaxial growth of rutile TiO₂ nanorods. The superior wettabilities of the TiO₂ nanorods resulted from treatments of vacuum and ultraviolet show great potential for applications in orthopaedic, dental implants, and possible photocatalysis.     

Self-assembled 3D flower-like NaY(MoO4)2:Eu microarchitectures: Hydrothermal synthesis, formation mechanism and luminescence properties

Self-assembled 3D flower-like NaY(MoO₄)₂:Eu³⁺ microarchitectures were successfully synthesized by a glycine-assisted hydrothermal method at 180 °C. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and high resolution transmission electron microscopy (HRTEM) were employed to characterize the as-obtained products. It was found that morphology modulation could be easily realized by changing the time of hydrothermal reaction system. 3D flower-like NaY(MoO₄)₂:Eu³⁺ microarchitectures were formed with 72 h reaction time. The formation mechanism for flower-like architecture was proposed on the basis of a series of time-dependent experiments. The NaY(MoO₄)₂:Eu³⁺ powders obtained can be effectively excited by 396 nm light, and exhibit strong red emission around 615 nm, attributed to the Eu³⁺⁵D₀ → ⁷F₂ transition. An investigation on the photoluminescence (PL) properties of NaY(MoO₄)₂:Eu³⁺ obtained revealed that the luminescence properties were correlated with the morphology and size.     

Effect of lattice-mismatch strain on the structural and dielectric properties of (Pb,Sr)TiO3 thin films grown by pulsed laser deposition

Pb_0.35Sr_0.65TiO₃ (PST) thin films have been fabricated on LaAlO₃ (LAO) and MgO substrates using the pulsed laser deposition technique. The microstructure characteristics of the films were examined by means of X-ray diffraction, atomic force microscopy, scanning electron microscopy and Raman spectroscopy, and the results indicate that the films are epitaxially grown and show good crystallinity. The dielectric constant dependence on DC bias voltage and temperature were measured in a planar capacitor configuration for these films. Compared to the PST thin film grown on LAO, the film grown on MgO showed a higher temperature of the capacitance maximum and a higher dielectric constant at zero bias. We explain the results by taking into account the lattice-mismatch strain between the substrate and the film. In contrast to the in-plane compressive strain induced by the LAO substrate, the in-plane tensile strain induced by the MgO substrate enlarges the unit cell of PST and enhances the magnitude of dipole moments, which increases the dielectric constant. These results indicate that a reasonable in-plane tensile strain could improve the dielectric properties of PST thin films.     

Hydrothermal synthesis of single-crystal BaTiO3 dendrites

In this paper, we report a simple hydrothermal method without any surfactants, for the first time, to synthesize single-crystal BaTiO₃ dendrites. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), electron diffraction (ED), and high-resolution transmission electron microscopy (HRTEM). The KOH concentration was found to be vital to the final formation of BaTiO₃ dendrites. An obvious morphology evolution from sphere-like shape to dendrite was observed when KOH concentration was decreased from 1 M to 0.1 M. It is rational to expect that dendritic structures of other perovskite oxides may also be synthesized by this simple method.     

One-pot synthesis of intestine-like SnO2/TiO2 hollow nanostructures

In the present study the intestine-like binary SnO₂/TiO₂ hollow nanostructures are one-pot synthesized in aqueous phase at room temperature via a colloid seeded deposition process in which the intestine-like hollow SnO₂ spheres and Ti(SO₄)₂ are used as colloid seeds and Ti-source, respectively. The novel core (SnO₂ hollow sphere)-shell (TiO₂) nanostructures possess a large surface area of 122 m²/g (calcined at 350 °C) and a high exposure of TiO₂ surface. The structural change of TiO₂ shell at different temperatures was investigated by means of X-ray diffraction and Raman spectroscopy. It was observed that the rutile TiO₂ could form even at room temperature due to the presence of SnO₂ core and the unique core-shell interaction.     

Hydrothermal synthesis, characterization and properties of TiO2 nanorods on boron-doped diamond film

The rutile TiO₂ nanorods have been hydrothermally synthesized on boron-doped diamond (BDD) film with a ZnO buffer layer. It is demonstrated that the ZnO buffer layer plays a key role in increasing the density and improving the morphology of synthesized TiO₂ nanorods. The heterojunction of n-TiO₂ nanorods/p-BDD shows an evident rectifying behavior with a ratio of ∼ 180 at 6 V. Experimentally, the TiO₂ nanorod-covered BDD exhibits an improved electron field-emission property over that without using a ZnO buffer layer.     

Pt纳米颗粒负载SrTiO3/TiO2异质结结构制备及制氢性能

本文以固定n(Sr)/n(Ti)摩尔比0.4的SrTiO_3/TiO_2(金红石相)异质结纳米颗粒,通过"光催化还原沉积方法"制备不同质量分数的纳米铂颗粒(0、1%、2%、5%),探究其催化活性的变化,采用XRD、SEM、UV-vis、XPS方法对其进行表征,并做了相关光催化分解水产氢性能测试.结果表明:负载贵金属Pt纳米颗粒量越大,对应的Pt晶粒平均尺寸为40.8 nm,1%Pt纳米颗粒SrTiO_3/TiO_2异质结构的BET比表面积在23.195 m~2/g处最高,并且介孔材料的特征是平均Barrett-Joyner-Halenda(BJH)孔径为13.60 nm,总孔体积为0.079 cm~3/g;高BET表面积和大的总孔体积强烈地支持SrTiO_3/TiO_2具有介孔结构的事实;相应的催化剂催化活性越高,其中负载5%Pt纳米颗粒的SrTiO_3/TiO_2纳米颗粒光催化8 h产氢量为3.574 mmol,平均产氢效率为0.447 mmol/(gcat·h),但从性价比的角度来考虑,其催化效率远不及负载1%Pt纳米颗粒的SrTiO_3/TiO_2纳米颗粒催化效率的5倍,因此负载5%Pt的SrTiO_3/TiO_2纳米颗粒光催化效率最高.     

Unique crystallization and formation of nonlinear optical (Na,K)NbO3 phases in (Na,K)NbGeO5 glasses

Crystalline phases and second-order optical nonlinearities in crystallized glasses of (Na,K)NbGeO₅ (i.e., xNa₂O · (25−x)K₂O · 25Nb₂O₅ · 50GeO₂) are examined. The molar volume of the glasses decreases with increasing Na₂O content, indicating that the glass structure of NaNbGeO₅ glass is more compact compared with KNbGeO₅ glass. The optical basicity of the glasses is 0.94–0.95, implying that chemical bonds among constituents ions are basically very ionic. (Na,K)NbGeO₅ glasses exhibit a unique crystallization depending on the Na₂O/K₂O ratio. The main crystalline phase in crystallized NaNbGeO₅ glass is the NaNbGeO₅ phase. KNbGeO₅ glass shows a prominent bulk nanocrystallization giving nanocrystals of the K_3.8Nb₅Ge₃O_20.4 phase. A glass with the composition of K_3.8Nb₅Ge₃O_20.4 also shows a bulk nanocrystallization. The crystallized glasses with K_3.8Nb₅Ge₃O_20.4 and NaNbGeO₅ crystalline phases do not show a second harmonic generation (SHG) at room temperature. The nonlinear optical (Na,K)NbO₃ phases showing a SHG are formed at the surface (5 μm) of crystallized glasses with x=15 and 20, giving an orientation of the (1 1 0) plane. The present study suggests the presence of mixed-alkali effect in the crystallization behavior of (Na,K)NbGeO₅ glasses.     

Hydrothermal synthesis of CeO2 nano-octahedrons

CeO₂ nano-octahedrons were synthesized with a facile hydrothermal synthesis process where Ce(NO₃)₃·6H₂O and urea were used as a cerium resource and mineralizer respectively and no surfactant or template was applied. The effects of synthesis parameters such as reaction temperature, reaction time, as well as the dosages of Ce (NO₃)₃·6H₂O and urea were studied. X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) analysis were conducted to characterize the crystalline and morphology of the obtained CeO₂ powders. The optimal reaction condition to prepare the CeO₂ of the desired fluorite structure was established. The possible mechanism of synthesis of CeO₂ with a nano-octahedron morphology was illustrated.     

The investigation of (Bi,La)(Ga,Fe)O3-PbTiO3 thin film prepared by PLD technique

In this report, (Bi,La)(Ga,Fe)O₃-PbTiO₃ (BLGF-PT) thin film was prepared on platinum coated Si wafer by pulsed laser deposition (PLD) method. BLGF-PT ceramic with morphotropic phase boundary (MPB) composition was used as the PLD target. The spot of Bi₂Fe₄O₉ impurity phase in X-ray diffraction profile implies a composition deviation in the BLGF-PT thin film from that of target. However, the MPB feature of co-existence of rhombohedral and tetragonal phases remains remarkable in the film. The characterization results of the leakage current and ferroelectric hysteresis loop indicate a desirable insulation in this BLGF-PT thin film. Polarization response by positive-up-negative-down pulse measurement and retention property are further carried out at room temperature to check the intrinsic ferroelectric performance. Moreover, high Curie temperature of 465 °C has been discovered in this BLGF-PT thin film, which may promote the application scope of the thin film.     

Effect of lead on formation and dielectric tunability of (Pbx,Sr1? x )0.85Bi0.1TiO3 thin films

(Pb_x,Sr_1−x )_0.85Bi_0.1TiO₃ thin films with the perovskite phase structure were prepared on an ITO glass substrate by sol-gel method. X-ray diffraction (XRD), scanning electron microscopy (SEM) and an impedance analyzer were respectively used in order to characterize the phase status, morphology and dielectric properties of the thin films. The results show that during the formation process of (Pb_x,Sr_1−x )_0.85Bi_0.1TiO₃ thin films, the nucleus of the perovskite phase are initially formed and then congregated. These aggregated nucleus are then transformed as the perovskite-phase crystalline in the thin film. Finally, the crystalline phase grows and separates gradually to form the perfect crystalline-phase structure. The content of the perovskite phase formed in the thin film under rapid thermal process (RTP) is more than that formed under traditional heat treatment with kinetic equilibrium. This is due to the high active decomposed ions that form the perovskite phase directly when heat-treated by RTP. The formation of the perovskite phase therefore overcomes a much lower barrier under RTP than that under traditional calcinations. The structure of the perovskite phase has a close relation to the ratio of Pb/Sr in the system because of the radius difference between Pb²⁺ and Sr²⁺. The transformation temperature between the cubic and the tetragonal structures of the perovskite phase increases with increasing Pb²⁺ content because the radius of Pb²⁺ is larger than that of Sr²⁺. It appears at room temperature when the content of Pb²⁺/Sr²⁺ is about 40/60 in the thin film. Meanwhile, the tetragonality of the perovskite phase is increased when Pb²⁺ ions increase due to its high polarization. The higher tunability of the (Pb_x,Sr_1−x )_0.85Bi_0.1TiO₃ thin film is exhibited when the film composition is close to the transformation point between the paraelectric and ferroelectric phases. Pb²⁺ ions show a dominant factor to affect the Curie point of the system and then changing tunability. Translated from Journal of Inorganic Materials, 2006, 21(2): 466–472 [译自: 无机材料学报]     

碳纳米管修饰LaFeO3/TiO2复合材料的光催化性能与机理

采用超声辅助溶胶凝胶法制备了LaFeO₃颗粒,进一步以碳纳米管(CNTs)为基底和钛酸丁酯为前体,通过一步水热法煅烧合成CNTs/TiO₂/LaFeO₃(CTF)三元异质结光催化复合材料。通过扫描电子显微镜(SEM)、X射线衍射分析(XRD)、氮气吸附-解吸等温线(BET)、紫外-可见分光光度计(UV-Vis)、光致发光光谱(PL)等表征手段对材料的形貌与特征结构、比表面积和孔径结构以及光学特征进行了分析,并在紫外光下通过降解活性黑五(RB5)测试样品的光催化性能。结果表明,以CNTs作为载体,能够有效提升LaFeO₃/TiO₂复合材料的光催化性能。当CNTs在复合材料中的质量占比为5%时,150 W汞灯照射下RB5的50 min去除率可达99.5%。CNTs一方面通过增加复合材料的比较面积为催化反应的进行提供了更多的活性位点,更为重要的是,CNTs作为光生载流子传输的通道加快了电荷分离效率,提升了复合材料的降解能力和催化反应动力学进程。