亚微米级Cu3(BTC)2的合成、表征及应用研究

采用水/溶剂热法合成了铜的亚微米级有机金属框架Cu_3(BTC)_2,并用扫描电镜、透射电镜、X射线粉末衍射、傅里叶红外光谱仪及光电子能谱仪对材料的形貌结构及表面性质进行了分析。将制备的Cu_3(BTC)_2用于吸附去除水中亚甲基蓝(MB)污染物。吸附结果表明,MB在Cu_3(BTC)_2上的吸附符合Freundlich模型。当MB初始浓度为30mg/L时,平衡吸附量为29.5mg/g,当初始浓度提高到300mg/L时,平衡吸附量达到244.3mg/g,吸附效果优于文献中报道的大部分吸附材料。     

Fabrication of Co3O4 cubic nanoframes: Facet-preferential chemical etching of Fe ions to Co3O4 nanocubes

The novel Co₃O₄ cubic nanoframes, sized in ca. 30 nm, were firstly fabricated via a facile solvothermal route. Based on the transmission electron microscopy and the powder X-ray diffraction analyses of the time-dependent products, a mechanism of facet-preferential chemical etching of Fe³⁺ ions to the pre-synthesized Co₃O₄ nanocubes is proposed for the formation of Co₃O₄ cubic nanoframes. This synthetic strategy can probably be extended to fabricate nanoframes of some other binary metal oxides, by designing similar chemical etching process.     

In situ fabrication of Bi2S3 nanocrystal film for photovoltaic devices

A facile wet-chemical method to prepare Bi₂S₃ thin films with flake nanostructures directly on ITO glass substrate is presented in this paper for the first time. The product was characterized by X-ray powder diffractometer (XRD), Raman spectrometer, scanning electron microscope (SEM), and atomic force microscope (AFM). The one-step solvothermal elements treatment on the ITO substrate spare time to form film by spin-coating process and the film could be tightly attached to the ITO electrode. A conjugated polymer, poly 3-hexylthiophene (P3HT), was then spin-coated on the as-prepared Bi₂S₃ film to form an inorganic-organic hybrid thin film. The photovoltaic performance of the resulting solar cell device was also investigated.     

Crystal-chemical anomalies in nonsuperconducting PrBa2Cu3O7

Studies of the crystal chemistry of nonsuperconducting PrBa₂Cu₃O₇ indicate that this compound is strictly isostructural with its superconducting RBa₂Cu₃O₇ (R = Y, rare earth) analogs. Crystallographically, Pr is present in the trivalent state according to the structural trends exhibited by the RBa₂Cu₃O₇ series as a function of R³⁺ ionic radius. The sole structural anomaly attributable to the presence of Pr³⁺ in the YBa₂Cu₃O₇ structure is a next-next-nearest neighbor effect and consists of an unusually short axial Cu-O distance, i.e., a short bond length between the in-plane copper and the chain oxygen. The correlation of this anomaly with the nonmetallic/nonsuperconducting properties of PrBa₂Cu₃O₇ supports a variety of literature reports, both theoretical and experimental, suggesting that the apical oxygen in the YBa₂Cu₃O₇ structure plays a critical role in mediating the appearance of superconductivity. The mechanism by which the f-electrons in Pr³⁺ (f ²) interact with the Cu-O manifold to produce the nonmetallic behavior of PrBa₂Cu₃O₇ remains unknown; however, superconductivity is turned back on for Nd³⁺ (f ³), immediately next to Pr and just slightly smaller. Careful comparative studies of superconducting NdBa₂Cu₃O₇ and nonmetallic PrBa₂Cu₃O₇ are needed to elucidate the critical difference in the behavior of the f-electrons and may shed light on the fundamental mechanism of high-temperature superconductivity in copper oxides.     

Microstructural study of YBa2Cu3O7/SrTiO3/YBa2Cu3O7 heteroepitaxial trilayer films grown on (100) SrTiO3 substrates

Detailed transmission electron microscopic study has been carried out on heteroepitaxial YBa₂Cu₃O₇/SrTiO₃/YBa₂Cu₃O₇ trilayer thin films grown on (100)SrTiO₃ substrates prepared by DC and RF magnetron sputtering. The microstructural results showed the existence of somea-axis-oriented YBCO grains 20–90 nm wide in thec-axis-oriented YBCO matrix. Some of thea-axis grains in the lower YBCO thin film layer have protruded into the above SrTiO₃ layer, which may cause short circuit between the two YBCO superconducting layers. This is unsuitable for the application of trilayer thin films for microelectronic devices. The defects on the surface of the substrates would also influence the growth quality of the YBCO thin films.     

Preparation and photoelectrochemical performance of TiO2/HS-CH2-COOH/Cu3Se2 composite film

In this paper, the TiO₂/HS-CH₂-COOH/Cu₃Se₂ composite film photoanodes were fabricated on conducting glass plates. Cu₃Se₂ nanoparticles were used as the sensitizer and the bi-functional modifier HS-CH₂-COOH was used at the interface between Cu₃Se₂ and TiO₂ films to improve the properties of the film photoanode. The characterization results show that the sol-gel prepared anatase TiO₂ film has a compact and uniform surface, while the tetragonal Cu₃Se₂ film has a coarse surface which is made up of uniform elongated particles. The photoelectrochemical experimental results indicate that the TiO₂/HS-CH₂-COOH/Cu₃Se₂ composite film photoanodes have a good photovoltaic property.     

Biomolecule-assisted Solvothermal Synthesis of Bismuth Sulfide Nanorods

A simple biomolecule-assisted synthetic route has been successfully developed to prepare bismuth sulfide(Bi 2 S 3 ) nanorods under solvothermal conditions.In the synthetic system,pentahydrate bismuth nitrate was employed to supply Bi source and L-cystine was used as sulfide source and complexing agent.The morphology,structure,and phase composition of the as-prepared Bi 2 S 3 products were characterized by X-ray diffraction(XRD),energy dispersion spectroscopy(EDS),X-ray photoelectron spectroscopy(XPS),field-...     

Synthesis and characterization of novel nanostructured fishbone-like Cu(OH)2 and CuO from Cu4SO4(OH)6

The Cu₄SO₄(OH)₆ was synthesized by a simple hydrothermal reaction with a yield of ~ 90%. Using Cu₄SO₄(OH)₆ as the starting material, novel fishbone-like Cu(OH)₂ was produced by a direct reaction of Cu₄SO₄(OH)₆ with NaOH solution. The Cu(OH)₂ consists of many needle-like nanorods parallel to each other and perpendicular to the direction of backbone, forming fishbone-like structure. Using the fishbone-like Cu(OH)₂ as the sacrificial precursor, CuO with similar size and morphology was obtained through a simple heat treatment. X-ray diffraction, scanning electron microscopy, energy dispersive X-ray, X-ray photoelectron spectroscopy, BET nitrogen adsorption, and UV-Vis absorption spectroscopy were employed to characterize the as-prepared samples. The conversion of the Cu₄SO₄(OH)₆ to the fishbone-like Cu(OH)₂ was visualized by time-dependent SEM images. A mechanism was also proposed based on the observed results.     

Superconductivity at differentTc in CdBa2Ca2Cu3Oy

A Cd analogue of the Tl and Hgn =3 series with nominal composition CdBa₂Ca₂Cu₃O_y has been synthesized. The samples were superconducting according to magnetic susceptibility measurements. The critical temperature was 103 or 107 K depending on the preparation conditions. The EDX analysis revealed the presence of Cd-1111, Cd-1121, and Cd-2333 as minor phases. The observed diamagnetic effects were attributed to the differentT _c of these phases.     

Synthesis and Processing of Doped Hg1Ba2Ca2Cu3Oy Superconductors

A series of quenching experiments were conducted to understand the sequence of reactions that occur during the synthesis of doped Hg1223, (Hg, A)Ba₂Ca₂Cu₃O _y , A = Re, Bi, and Pb (HgA1223). The formation and decomposition of the intermediate phases during the high-temperature reaction were followed as a function of temperature. HgA1223 phase forms over a wide range of temperatures, 750–950°C, 750–880°C, and 840–880°C for A = Re, Pb, and Bi, respectively. At T<750°C, HgA1212 phase forms for A = Re and Pb. Based on the results of quenching experiments, heat treatment conditions were optimized for the synthesis of pure HgA1223 phase using commercial BaCaCuO precursor powders. A reduced-temperature annealing stage after the high-temperature reaction helps in grain growth and improves the microstructural characteristics of HgA1223 samples. Control of Hg pressure during the reaction is crucial for achieving phase purity, grain growth, and texture in the final products. A novel approach for the control of Hg pressure during the synthesis of HgA1223, which consists of using CaHgO₂ as an external Hg source, is reported. HgA1223 samples synthesized using the new synthesis protocol exhibit improved microstructural and superconducting properties.     

Vortex motion in coupled DyBa2Cu3O7/(Y0.6Pr0.4)Ba2Cu3O7 heterostructures

Multilayer structures containing 24 Å thick DyBa₂Cu₃O₇ layers, separated by 96 Å of an (Y_0.6Pr_0.4)Ba₂Cu₃O₇ alloy, are studied to investigate the effect of coupling on vortex dynamics. With the magnetic field perpendicular to theab plane, and as a function of the number of superconducting layers in the structure, we find that the activation energy for flux motion increases, first linearly, and then saturates. This linear increase is taken as evidence that pancake vortices belonging to different DyBa₂Cu₃O₇ layers are stacked and have a coupled motion. Above a characteristic number of superconducting layers,N _c , shear of the vortex structures becomes important and the thermally activated process only displaces a stack ofN _c pancake vortices, meaning that the vortex lattice is turning three dimensional. In these structures we findN _c to be 2 to 3.     

Charge-transfer in YBa2Cu3Ox

The charge-transfer hypothesis is shown to be inconsistent with data for YBa₂Cu₃O_x: (i) The two-step behavior ofT _c(x) (with jumps from zero to 60 K and then to 90 K) is not reflected as a similar, statistically significant two-step behavior in the bond-valence-sum charge of cuprate-plane Cu ions (as once believed), (ii) as a consequence of the law of conservation of charge, the derivatives of the layer charges with respect to oxygen contentx for both the Ba-O layers and the charge-reservoir Cu-O chains have the opposite signs to those predicted, and (iii) the charge-transfer observed for superconducting YBa₂Cu₃O_x is not sufficient to produce superconductivity, as demonstrated by insulating PrBa₂Cu₃O_x, which has virtually the same layer charges.     

Thin film solar cells based on the ternary compound Cu2SnS3

Alongside with Cu₂ZnSnS₄ and SnS, the p-type semiconductor Cu₂SnS₃ also consists of only Earth abundant and low-cost elements and shows comparable opto-electronic properties, with respect to Cu₂ZnSnS₄ and SnS, making it a promising candidate for photovoltaic applications of the future. In this work, the ternary compound has been produced via the annealing of an electrodeposited precursor in a sulfur and tin sulfide environment. The obtained absorber layer has been structurally investigated by X-ray diffraction and results indicate the crystal structure to be monoclinic. Its optical properties have been measured via photoluminescence, where an asymmetric peak at 0.95 eV has been found. The evaluation of the photoluminescence spectrum indicates a band gap of 0.93 eV which agrees well with the results from the external quantum efficiency. Furthermore, this semiconductor layer has been processed into a photovoltaic device with a power conversion efficiency of 0.54%, a short circuit current of 17.1 mA/cm², an open circuit voltage of 104 mV hampered by a small shunt resistance, a fill factor of 30.4%, and a maximal external quantum efficiency of just less than 60%. In addition, the potential of this Cu₂SnS₃ absorber layer for photovoltaic applications is discussed.     

Raman scattering studies of ultrathin-layer YBa2Cu3O7/PrBa2Cu3O7 superlattices

We present Raman scattering studies ofc-oriented ultrathin-layer superconducting (YBa₂Cu₃O₇) _m /(PrBa₂Cu₃O₇) _n superlattices. For the superlattice with (m=2,n=1) sequence, Raman spectra reveal a new line in the spectral region around 320 cm^–1. It is interpreted as a mode representing a combination of IR optical phonons of the Y-sublayers with an admixture of aB _1g type Raman active vibration in the Pr sublayers. This new line, which is similar to those from the interior of the Brillouin zone of the original lattice, does not exhibit superconductivity-induced self-energy effects, although its counterpart in the pure substance does. No additional line is found in the (m=1,n=2) superlattice in the same region, supporting our interpretation for the (m=2,n=1) sample.     

Solvothermal synthesis of In(OH)3 nanorods and their conversion to In2O3

In this work, we demonstrate that monodisperse indium hydroxide (In(OH)₃) nanorods constructed with parallel wire-like subunits have been fabricated via a acrylamide-assisted synthesis route without any template. NH₃ from the hydrolysis of acrylamide acts as the OH⁻ provider. The structure and morphology of as-prepared products have been characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM) and thermogravimetric analysis (TG). A detailed mechanism has been proposed on the basis of time-dependent experimental results. Furthermore, by annealing In(OH)₃ precursors at 500 °C for 3 h in air, In₂O₃ samples were obtained with the designed morphology.     

Single-step sputtered Cu2SnSe3 films using the targets composed of Cu2Se and SnSe2

Cu₂SnSe₃ thin films were prepared by single-step D.C. sputtering at 100-400 °C for 3 h using targets composed of Cu₂Se and SnSe₂ in three different ratios of 2/1 (target A), 1.8/1 (target B), and 1.6/1 (target C). The advantages of self-synthesized SnSe₂ instead of commercially available SnSe for depositing Cu₂SnSe₃ thin films were demonstrated. Effects of target composition and substrate temperature on the properties of Cu₂SnSe₃ thin films were investigated. Structure, surface morphology, composition, electrical and optical properties at different process conditions were measured. The 400 °C-sputtered films obtained from target B display with direct band gap of 0.76 eV, electrical resistivity of 0.12 Ω cm, absorption coefficient of 10⁴-10⁵ cm^− 1, carrier concentration of ∼ 1.8 × 10¹⁹ cm^− 3, and electrical mobility of 2.9 cm²/V s.     

Synthesis of (Hg,X)Ba2Ca2Cu3Ox Superconductors

Synthesis and processing parameters for (Hg_1–xBi_x)Ba₂Ca₂Cu_3.1O_y were optimized for growth at temperatures suitable for growth on Ag and Au substrates (<850° C). Use of Bi₂CuO₄ as a Bi source combined with variations of BaCaCuO precursor phase assemblages allowed the formation of some liquid phase during the reaction and resulted in dense (Hg_1–xBi_x)Ba₂Ca₂Cu_3.1O_y samples with aligned colonies of grains. Magnetization measurements in fields up to 30 T indicated good intergrain coupling within the large grain colonies. The results of the Bi doped samples are compared with those of previously reported Re doped samples.     

Synthesis and characterization of bundle-like structures consisting of single crystal Ce(OH)CO3 nanorods

Bundle-like structures consisting of single crystal cerium hydroxide carbonate (Ce(OH)CO₃) nanorods have been synthesized successfully by a hydrothermal method at 100 °C using cerium nitrate (Ce(NO₃)₃·6H₂O) as the cerium source, aqueous carbamide both as an alkaline and carbon source and cetyltrimethylammonium bromide (CTAB) as surfactant. X-ray powder diffraction (XRD), field-emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM) were used to characterize such bundle-like structures. SEM and TEM images show that Ce(OH)CO₃ bundle-like structures were composed of nanorods with diameters of ∼ 100 nm. The XRD pattern and electron diffraction (ED) pattern indicate that Ce(OH)CO₃ has a pure orthorhombic single crystal structure.     

Development of random access memory in Nd0.7Ca0.3MnO3/YBa2Cu3O7 heterostructure

The effects of electrode on the resistive switching in Nd_0.7Ca_0.3MnO₃(NCMO)/YBa₂Cu₃O₇(YBCO) heterostructure are investigated at room temperature. For Cu/NCMO/YBCO, resistance can be switched on-and-off from a high- to low-resistance state at a steady ratio of 25% with a pulsed-voltage of ± 3 V. On the other hand, a giant resistance-change as large as 1350% is observed with ± 5 V for Ag/NCMO/YBCO with a fast decay down to 550%. Our experimental results show clear evidences that the nature of interfaces can be modified by the electric field and it dictates the resistive switching behavior of these heterostructure devices, which are the potential candidates for the random access memory.     

Magnetization and Susceptibility Studies on BaZrO3-Doped YBa2Cu3O7 ? x Bulk Superconductors

We studied the YBa₂Cu₃O_{7 – x} bulk superconductor doped with BaZrO₃ up to 50 wt.%, obtained by solid-state reaction powder technology. From DC magnetization loops and low frequency AC susceptibility measurements we determined the influence of the BaZrO₃ doping level on the critical temperature, critical current density, field for full penetration, and intergrain lower critical field. The results show that even high content of BaZrO₃ does not lead to degradation of the superconducting properties of bulk YBa₂Cu₃O_{7 – x} .