通过超宽139La固体核磁共振波谱研究层状La(OH)2NO3

层状稀土氢氧化物是一类新型的稀土功能材料,本文采用固体核磁共振（SSNMR）方法研究了同时具备离子交换能力和非线性光学特性的层状La（OH）₂NO₃化合物,探讨了通过四极核CPMG（QCPMG）脉冲序列和变频谱图采集获取超宽¹³⁹La SSNMR谱图的方法,并描述了适用于此类实验的滤波方程和谱图重建方法.重建谱图同时包含四极核中心跃迁和卫星跃迁信息,本文使用QUEST软件对超宽¹³⁹La NMR谱图进行了模拟,获取的四极耦合常数C_Q和非对称因子η_Q均与CASTEP密度泛函理论计算值高度吻合.SSNMR实验结果证实层状La（OH）₂NO₃化合物属于非中心对称结构（P2₁）,解决了对其结构长期以来存在的争论.     

Hydrothermal Synthesis at High Pressure and Temperature of the Mg 7.5 Ni 6 H 3 (AsO 4 ) 8 (OH) 6 and Mg 8 Ni 4 H 6 (PO 4 ) 8 (OH) 6 Compounds

The Mg 7.5 Ni 6 H 3 (AsO 4 ) 8 (OH) 6 and Mg 8 Ni 4 H 6 (PO 4 ) 8 (OH) 6 compounds have been synthesized by using hydrothermal techniques at high pressure and temperature. The crystal structure of the arsenate phase has been refined with the Rietveld method. The compounds are isostructural. The structure consists of a three-dimensional framework in which the presence of triangular and hexagonal channels is observed. Reflectance diffuse measurements confirm the hexacoordination of the Ni(II) ions in both compounds. The magnetic behaviour indicates the presence of antiferromagnetic interactions between the Ni(II) ions placed in the double chains.     

Preparation,characterization, and electrochemical performances of graphene/Ni(OH)2 hybrid nanomaterials

We report a class of core–shell nanomaterials that can be used as efficient surface-enhancement Raman scattering (SERS) substrates. The core consists of silver nanowires, prepared through a chemical reduction process, that are used to capture 4-mercaptobenzoic acid (4-MBA), a model analyte. The shell was prepared through a modified Stöber method and consists of patchy or full silica coats. The formation of silica coats was monitored via transmission electron microscopy, UV–visible spectroscopy, and phase-analysis light-scattering for measuring effective surface charge. Surprisingly, the patchy silica-coated silver nanowires are better SERS substrate than silver nanowires; nanomolar concentration of 4-MBA can be detected. In addition, “nano-matryoshka” configurations were used to quantitate/explore the effect of the electromagnetic field at the tips of the nanowire (“hot spots”) in the Raman scattering experiment.     

Ni2(OCH3)2/SiO2催化剂上CO2和CH3OH的吸附和反应性能

采用表面改性和离子交换相结合的方法制备了Ni2 (OCH3 ) 2 /SiO2 负载型双核金属甲氧基配合物催化剂 ,利用红外光谱 (IR)、程序升温脱附 (TPD)、程序升温表面反应 (TPSR)和微反技术考察了催化剂的表面结构以及CO2 和CH3 OH的化学吸附和反应性能 .结果表明 :Ni2 (OCH3 ) 2 /SiO2 中Ni2 + 与载体SiO2 表面O2 -以双齿配位形式键合 ,甲氧基以桥基形式联结双金属离子形成双核物种Ni2 (OCH3 ) 2 ;CO2 在催化剂表面存在甲氧碳酸酯基物种和桥式两种吸附态 ,CH3 OH则只有一种分子吸附态 ;在 10 0～ 2 0 0℃条件下 ,CO2 和CH3 OH在催化剂上的反应产物主要是DMC和H2 O ;根据反应结果 ,讨论了催化反应机理 .     

Synthesis and characterization of Gd(OH)3 nanobundles

Gd(OH)₃ nanobundles, which consisted of bundle-like nanorods, have been prepared through a simple and facile hydrothermal method. The crystal, purity, morphology and structural features of Gd(OH)₃ nanobundles are investigated by powder X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED) and energy dispersive X-ray (EDX). A possible formation mechanism of Gd(OH)₃ nanobundles is briefly discussed.     

Effect of the La(OH)3 preparation method on the surface and rehydroxylation properties of resulting La2O3 nanoparticles

In the present study, for the first time, Cu₃N/NiTiCu/Si heterostructures were successfully grown using magnetron sputtering technique. Nanocrystalline copper nitride (Cu₃N with thickness ~200 nm) thin films and copper nanodots were subsequently deposited on the surface of 2-μm-thick NiTiCu shape memory thin films in order to improve the surface corrosion and nickel release properties of NiTiCu thin films. Interestingly, the phase transformation from martensite phase to austenite phase has been observed in Cu₃N/NiTiCu heterostructures with corresponding change in texture and surface morphology of top Cu₃N films. Field emission scanning electron microscopy and atomic force microscope images of the heterostructures reveals the formation of 20-nm-sized copper nanodots on NiTiCu surface at higher deposition temperature (450 °C) of Cu₃N. Cu₃N passivated NiTiCu films possess low corrosion current density with higher corrosion potential and, therefore, better corrosion resistance as compared to pure NiTiCu films. The concentration of Ni released from the Cu₃N/NiTiCu samples was observed to be much less than that of pure NiTiCu film. It can be reduced to the factor of about one-ninth after the surface passivation resulting in smooth, homogeneous and highly corrosion resistant surface. The antibacterial and cytotoxicity of pure and Cu₃N coated NiTiCu thin films were investigated through green fluorescent protein expressing E. coli bacteria and human embryonic kidney cells. The results show the strong antibacterial property and non cytotoxicity of Cu₃N/NiTiCu heterostructure. This work is of immense technological importance due to variety of BioMEMS applications.     

Mn5(PO3(OH))2(PO4)2(H2O)4的水热合成和光谱研究

在水热反应条件下合成出具有红磷锰矿结构的Mn5(PO3(OH) ) 2 (PO4 ) 2 (H2 O) 4单晶 ,在X ray单晶结构分析的基础上 ,对其固体紫外可见漫反射光谱、红外光谱、荧光光谱和热重光谱进行了研究。结果表明 ,构成该化合物的PO4 四面体及MnO6 八面体通过共顶点或共棱方式相连接 ,与P ,Mn配位的氧分为 3类 :即端基氧 (Od)、二桥氧 (Ob)和三桥氧 (Oc)。因而在 2 10和 2 5 0nm左右出现了Od→Mn和Ob ,c→Mn的荷移跃迁吸收谱带 ;在 10 0 0～ 110 0cm- 1 处 ,P—O的伸缩振动峰分裂为 3个 ;70 0～ 980cm- 1 处存在 3类Mn—O的伸缩振动。对标题化合物分别采用 2 18和 310nm的光激发 ,分别在 35 4和 4 13nm产生强而尖锐的荧光光谱发射峰 ,表现了很强的光学效应。热重分析表明该化合物在 2 70℃以下结构保持稳定 ,在 2 70～36 0℃范围内失去配位水。量化计算得单点能为 - 4 5 5 8 6 5 95 5 5 1a u ;前线轨道能量HOMO(Alpha) =- 0 2 80 80a u ,LOMO(Alpha) =0 0 15 2 7a u ,能隙为 0 2 96 0 7a u ;HOMO(Beta) =- 0 2 5 919a u ,LOMO(Beta)=0 0 0 10 8a u ,能隙为 0 2 6 0 72a u ;偶极矩为 4 2 0 82Debye。     

Hydrothermal route to VO<Subscript>2</Subscript> (B) nanorods: controlled synthesis and characterization

One-dimensional vanadium dioxides have attracted intensive attention owing to their distinctive structure and novel applications in catalysis, high energy lithium-ion batteries, chemical sensors/actuators and electrochemical devices etc. In this paper, large-scale VO₂ (B) nanorods have been successfully synthesized via a versatile and environment friendly hydrothermal strategy using V₂O₅ as vanadium source and carbohydrates/alcohols as reductant. The obtained samples are characterized by XRD, FT-IR, TEM, and XPS techniques to investigate the effects of chemical parameters such as reductants, temperature, and time of synthesis on the structure and morphology of products. Results show that pure B phase VO₂ with homogeneous nanorod-like morphology can be prepared easily at 180 °C for 3 days with glycerol as reluctant. Typically, the nanorod-like products are 0.5–1 μm long and 50 nm width. Furthermore, it is also confirmed that the products are consisted of VO₂, corresponding to the B phase. More importantly, this novel approach is efficient, free of any harmful solvents and surfactants. Therefore, this efficient, green, and cost-saving route will have great potential in the large-scale fabrication of 1D VO₂ (B) nanorods from the economic and environmental point of view.     

Preparation and magnetic characterization of Co2-W strontium hexaferrites doped with Ni and La

The formation and magnetic properties of new Ni- and La-substituted SrCo₂-W hexaferrites were investigated. Fabrication of single phase samples required undertaking composition and sintering conditions optimization. This process confirmed the production of W hexaferrites from intermediate cubic and hexagonal ferrite phases and additionally proved the enhancement of final purity by the excessive hexagonal component. Furthermore, according to the X-ray diffraction analysis, pure Ni- or La-doped compounds were formed in most cases, which actually necessitated more intense heat treatment (1225–1250 °C). Yet, magnetic measurements interestingly reveal that substances with low substitution possess high saturation magnetization (～72–75 Am²/kg) and unexpectedly lower coercivity (～28–46 Oe), compared to the undoped one. This behavior is attributed to the chemistry of both substitutions, inducing the magnetic order variation and the anisotropy transition from in-plane to axial. Thus, a scarcely elaborated transient compositional region with planar anisotropy and strong magnetization is discerned, highlighting the potential of these soft ferrites.     

Hydrothermal synthesis, characterization and Raman studies of Eu activated Gd2O3 nanorods

Eu³⁺ (8 mol%) activated gadolinium oxide nanorods have been prepared by hydrothermal method without and with surfactant, cityl trimethyl ammonium bromide (CTAB). Powder X-ray diffraction (PXRD) studies reveal that the as-formed product is in hexagonal Gd(OH)₃:Eu phase and subsequent heat treatment at 350 and 600 °C transforms the sample to monoclinic GdOOH:Eu and cubic Gd₂O₃:Eu phases, respectively. The structural data and refinement parameters for cubic Gd₂O₃:Eu nanorods were calculated by the Rietveld refinement. SEM and TEM micrographs show that as-obtained Gd(OH)₃:Eu consists of uniform nanorods in high yield with uniform diameters of about 15 nm and lengths of about 50-150 nm. The temperature dependent morphological evolution of Gd₂O₃:Eu without and with CTAB surfactant was studied. FTIR studies reveal that CTAB surfactant plays an important role in converting cubic Gd₂O₃:Eu to hexagonal Gd(OH)₃:Eu. The strong and intense Raman peak at 489 cm⁻¹ has been assigned to A_g mode, which is attributed to the hexagonal phase of Gd₂O₃. The peak at ∼360 cm⁻¹ has been assigned to the combination of F_g and E_g modes, which is mainly attributed to the cubic Gd₂O₃ phase. The shift in frequency and broadening of the Raman modes have been attributed to the decrease in crystallite dimension to the nanometer scale as a result of phonon confinement.     

Self-assembled 3D La(OH)3 and La2O3 nanostructures: Fast microwave synthesis and characterization

Self-assembled three-dimensional (3D) urchin-like and flower-like La(OH)₃ nanostructures were successfully prepared for the first time via a facile and fast microwave-assisted solution-phase chemical method in 15 min. The obtained products were characterized by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). The SEM results reveal that the urchin-like and flower-like La(OH)₃ nanostructures are ca. 3 μm and 6 μm in diameter, respectively. The urchin-like La(OH)₃ nanostructures are constructed by nanorods with diameters of about 300 nm and lengths of about 500 nm. The flower-like La(OH)₃ nanostructures are built from nanopetals about 100 nm thick. The effects of reaction time, microwave power, amount of tetraethyl ammonium bromide (TEAB), and surfactants on the preparation were systematically investigated. The possible formation mechanism of the 3D La(OH)₃ nanostructures was preliminarily discussed. Urchin-like and flower-like La₂O₃ nanostructures were obtained after calcining the La(OH)₃ nanostructures at 800 °C for 4 h. Urchin-like and flower-like La₂O₃:Eu³⁺ nanostructures were also prepared and their photoluminescence (PL) properties were investigated.     

Hydrothermal synthesis, controlled microstructure, and photoluminescence of hydrated Zn3(PO4)2: Eu3+ nanorods and nanoparticles

In this article, Zn₃(PO₄)₂: Eu³⁺ nanorods and nanoparticles have been prepared by the hydrothermal method. The optimum pH value has been found at the range of 3–8 for the preparation of orthorhombic Zn₃(PO₄)₂: Eu³⁺, whose morphologies are affected by the pH value. At the same temperature for hydrothermal reaction, the product presents nanorods at pH 4, while it shows nanoparticles at pH 6. Furthermore, the influences of the hydrothermal reaction temperature on the morphology and microstructure have also been investigated, suggesting that the morphology and microstructure cannot be changed with the hydrothermal temperature at the same pH value. Finally, the photoluminescence of Eu³⁺ on Zn₃(PO₄) nanorod/nanoparticle have been studied, both of which present the characteristic emission lines of Eu³⁺ and the ⁵D₀–⁷F₁ transition corresponds the strongest emission. This indicates that Eu³⁺ occupied the inversion center in Zn₃(PO₄) host.     

Hydrothermal synthesis of C-doped Zn3(OH)2V2O7 nanorods and their photocatalytic properties under visible light illumination

A visible light-driven photocatalyst, C-doped Zn₃(OH)₂V₂O₇, prepared by a hydrothermal method was studied. The as-prepared catalyst was characterized by SEM, XRD, DRS, and XPS, and exhibited efficient photocatalytic activity in the degradation of methylene blue (MB) under visible-light irradiation. Besides decoloring, the decomposition of MB was also observed, further demonstrating the performance of the photocatalyst. The carbon existing on the surface of Zn₃(OH)₂V₂O₇ nanorods was free and in carbide form. Dye degradation followed first-order kinetics, and was explained on the basis of the Langmuir-Hinshelwood mechanism.     

Competitive growth of In2O3 nanorods with rectangular cross sections

In₂O₃ nanorods with rectangular cross sections have been successfully synthesized using Au as a catalyst through chemical vapor deposition methods. The synthesized nanorods possessed larger size than that of the catalyst particle. The growth process was discussed through detailed theory analysis and experimental validation, and a competitive growth model between axial growth under the vapor–liquid–solid (VLS) mechanism and lateral growth controlled by the vapor–solid (VS) mechanism was proposed to explain the formation of a rectangular cross section and the size change of the nanorods. The research regarding controlled growth under the two mechanisms, viz. VLS and VS, was beneficial for exploration into the controlled growth of complicated functional nanomaterials. Furthermore, the photoluminescence property was also studied. PACS  61.46.-W     

Kinetics of Ni2Si growth from pure Ni and Ni(V) films on (111) and (100) Si

The kinetics of Ni₂Si growth from pure Ni and from Ni_0.93V_0.07 films on (111) and (100) silicon has been studied by the combination of He⁺ backscattering, x-ray diffraction, Auger electron spectroscopy (AES) and transmission electron microscopy (TEM) techniques. The activation energies are 1.5 and 1.0 eV for pure Ni and Ni(V) films, respectively while the pre-exponential factors in Ni(V) are 4–5 orders of magnitude smaller than in the pure Ni case. The variations in the measured rates are related to the different grain size of the growing suicide layers. The vanadium is rejected from the silicide layer and piles up at the metalsilicide interface.     

Electronic structure and magnetism of La(4)Ni(3)O(8) from first principles

The magnetic and electronic properties of La(4)Ni(3)O(8) are investigated by performing the full-potential linearized augmented plane wave method. The C-type antiferromagnetic spin ordering is preferred and a molecular correlated insulating state with high-spin Ni ions is found. Our results have proved that this insulating state is caused by a correlation effect and the strong interlayer interaction. Such strong interlayer coupling results from the high-spin occupation of Ni ions.     

负载有MTiO_3(M=Sr或Ba)的TiO_2纳米棒复合材料的制备和表征

以Sr(OH)2或Ba(OH)2和TiO2纳米带为前驱物,通过水热反应直接制得了立方相MTiO3(M=Ba或Sr)纳米粒子负载的TiO2纳米复合材料。采用XRD,SEM,TEM,HRTEM和UV-Vis等测试手段对产物的组成、物相、形貌、结构和光学性质进行了详细表征。结果表明,Sr(OH)2或Ba(OH)2的加入量或反应时间皆对MTiO3纳米粒子负载量有较大影响,在一定程度上,氢氧化物加入量增多以及反应时间延长,纳米粒子负载量就会增大;无论是纯TiO2纳米带还是复合纳米棒,其吸收和发射光谱基本相同。对罗丹明B可见光催化降解实验结果证实,这些纳米复合材料皆有较高的光催化活性,远高于P-25的光降解活性。     

Flower-like Ni3(NO3)2(OH)4@Zr-metal organic framework (UiO-66) composites as electrode materials for high performance pseudocapacitors

Zr-metal organic frameworks (Zr-MOFs, UIO-66) as a kind of crystalline porous material possess controllable porous structure and strong thermal stability up to 753 K. In this paper, we synthesized Ni₃(NO₃)₂(OH)₄, Zr-MOF with high specific surface area (1073 m² g⁻¹) and Ni₃(NO₃)₂(OH)₄@Zr-MOF composite for pseudocapacitor material. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were taken to characterize the structure and morphology of Ni₃(NO₃)₂(OH)₄, Zr-MOF, and Ni₃(NO₃)₂(OH)₄@Zr-MOF. The porous structure of Zr-MOF favors the utilization of the active material Ni₃(NO₃)₂(OH)₄ and interfacial charge transport and provides short diffusion paths for ions, which results in a high specific capacitance. Electrochemical properties are evaluated by cyclic voltammetry (CV) and galvanostatic charge/discharge measurement. A maximum specific capacitance (SC) of 992 F/g was obtained from CV at a scan rate of 5 mVs⁻¹, which is higher than Zr-MOF (∼134 F g⁻¹) and Ni₃(NO₃)₂(OH)₄ (∼753 F g⁻¹). Meanwhile, the Ni₃(NO₃)₂(OH)₄@Zr-MOF composite electrode exhibits a good cycling stability over 3000 cycles.