掺银SnOx薄膜的催化作用

掺银ＳｎＯ_ｘ薄膜的催化作用张勇，周坤粦，曹伟民（中国科学院成都有机化学研究所成都６１００４１）关键词气敏薄膜，表面掺杂，催化ＳｎＯ２是重要的气敏传感材料，采用纳米技术，可使元件微型化、集成化，并可提高灵敏度。本文以等离子体增强化学气相沉积法制得超微?..     

Y2O3薄膜/锡掺杂玻璃光波导气敏元件及其气敏性

采用溶胶-凝胶法将氧化钇(Y2O3)敏感膜固定在锡掺杂玻璃光波导表面,研制出了Y2O3薄膜/锡掺杂玻璃光波导气敏元件,并对挥发性有机气体进行了检测.通过XRD测试对敏感薄膜的结构及晶粒尺寸进行了表征.实验结果表明,在室温下Y2O3薄膜/锡掺杂玻璃光波导气敏元件对二甲苯、氯苯气体有较好的选择性响应,其响应浓度范围为l×10-3 ～1×10-5(V/V).Y2O3薄膜/锡掺杂玻璃光波导气敏元件具有灵敏度高、成本低、响应速度快、制作工艺简单和可逆性好等优点.     

脉冲激光沉积掺杂二氧化硅的钴酸锂正极薄膜材料

采用脉冲激光溅射的方法成功制备了掺杂二氧化硅的钴酸锂薄膜电极。结合SEM, XRD,HRTEM,SAED,EDX,充放电,以及循环伏安等手段对其形貌,结构与电化学性能进行了研究。结果表明,掺杂了二氧化硅的钴酸锂电极薄膜在电化学反应的过程中具有结构刚性,放电平台稳定,极化较小等优点,因此可能成为一种优良的二次锂离子正极材料。     

Tin Oxide Thin Film with Three‐Dimensional Ordered Reticular Morphology as a Lithium Ion Battery Anode

Three‐dimensional (3D) reticular SnO₂ thin films deposited on copper and stainless steel substrates were prepared by the electrostatic spray deposition (ESD) technique. The 3D reticular SnO₂ film exhibit a high reversible capacity near 300 mAh g^?1 up to the 50th cycle.     

Flexible and Epitaxial Metal Oxide Thin Film Growth by Photoreaction Processing for Electrical and Optical Applications

This review summarizes the use of photoreactions that replace conventional heating processes for growing oxide thin films from chemical solutions. In particular, this review outlines key variables in photoreactions that affect epitaxial and polycrystalline thin film growth, including precursor materials, laser wavelength, laser fluence, and carbon. In addition, the features of the photoreaction process that can be controlled at a low temperature by oxygen non-stoichiometry are examined. Likewise, functions that are neither achieved by developing a gradient structure nor controlled by a thermal equilibrium reaction are detailed. Two new concepts are presented, known as photoreaction of nanoparticles (PRNP) and photoreaction of a hybrid solutions (PRHS), in which crystal nuclei are pre-dispersed in a metal–organic compound film. This method has successfully produced flexible phosphor films used as resistor or thermistor electronic components. Finally, thin film growth using different light sources such as flash lamps and femtosecond lasers (fs) is explored.     

Ni控制掺杂TiO2薄膜的光电化学及光催化活性

采用溶胶-凝胶法通过分步控制工艺制备了镍离子不同掺杂方式的TiO₂薄膜。通过甲基橙的光催化降解动力学来表征其光催化活性。结果表明：镍离子非均匀掺杂在掺杂量0.5%时可以明显增强TiO₂的光催化活性，而均匀掺杂提高TiO₂的光催化活性较小。光电化学表征结果显示：镍离子非均匀掺杂TiO₂薄膜的瞬时光电流信号较强，说明其光生载流子易于生成且分离效果较好；循环伏安曲线表明，光照时Ni非均匀掺杂的TiO₂薄膜改变了体系的氧化还原电位，说明了薄膜内建电场的建立。基于半导体的P-N结原理探讨了镍离子非均匀掺杂TiO₂薄膜的光催化活性机理。     

Propargyl Amine Synthesis Catalysed by Gold and Copper Thin Films by Using Microwave‐Assisted Continuous‐Flow Organic Synthesis (MACOS)

An effective multi‐component reaction (MCR) protocol has been developed for the construction of propargyl amines from aldehydes, amines and terminal alkynes by using microwave‐assisted continuous‐flow organic synthesis (MACOS). The process is catalysed by thin films of either copper or gold that achieve temperatures in excess of 900 °C when irradiated with low levels of microwave power. The process works equally well for premixed solutions of the three starting materials, or as three separate streams, which improves the combinatorial efficiency of the method. The process tolerates a wide variety of functional groups and heterocycles, and conversion over these diverse substrates ranges from 70–90 %.     

Enhanced Property of Thin Cuprous Oxide Film Prepared through Green Synthetic Route

Thin cuprous oxide films have been prepared by chemical vapor deposition (pulsed spray evaporation-chemical vapor deposition) method without post-treatment. The synthesis ofcuprous oxide was produced by applying a water strategy effect. Then, the effect of water on the morphology, topology, structure, optical properties and surface composition of the obtained films has been comprehensively investigated. The results reveal that a pure phase of Cu₂O was obtained. The introduction of a small quantity of water in the liquid feedstock lowers the band gap energy from 2.16 eV to 2.04 eV. This finding was mainly related to the decrease of crystallite size due to the effect of water. The topology analyses, by using atomic force microscope, also revealed that surface roughness decreases with water addition, namely more uniform covered surface. Moreover, theoretical calculations based on density functional theory method were performed to understand the adsorption and reaction behaviors of water and ethanol on the Cu₂O thin film surface. Formation mechanism of the Cu₂O thin film was also suggested and discussed.     

A Polarographic Method Determing Cu(II), Cu(I) and Metallic Copper Contents in Copper Oxide Samples

Abstract

A polarographic procedure was developed which permits the analysis of powdered cupric and cuprous oxides in the presence of metallic copper. To determine CuO, Cu₂O and metallic copper content in the sample two weight aliquots were used. The first aliquot was dissolved in medium of 50 % ethanol + 3 M hydrochloric acid + saturated ascorbic acid solution. Insoluable metallic copper was determined polarographically after its' separation and additional dissolving in concentrated nitric acid.

The second sample aliquot was dissolved in 6 M hydrochloric acid and the ratio of Cu(I) / Cu(II) in the solution was determined from the polarographic curves. To calculate CuO, Cu₂O and Cu content in a sample the proposed procedure was applied. The developed method provides the accurate results of the determination of CuO, Cu₂O and Cu content in a powdered mixture. The reproducibility expressed as the relative standard deviation is from 1 % to 5 %.     

铜卟啉,钒氧卟啉的合成

铜卟啉、钒氧卟啉的合成王煜，何明威，王军强，武靖荣（山西大学化学系太原０３０００６）关键词卟啉，铜卟啉，钒氧卟啉，合成合成金属卟啉，通常是先合成卟啉，再将卟啉与金属盐反应，经柱色谱分离后得到目标化合物［１］．本文报道以酚为溶剂，使吡咯、芳香醛和乙酸铜...     

Improved Thin‐Film Transistor Performance Through a Melt of Poly(para‐phenyleneethynylene)

The performance of polymer field‐effect transistors (PFETs) based on short rigid rod semiconducting poly(2,5‐didodecyloxy‐p‐phenyleneethynylene) (D‐OPPE) is highlighted. The controlled heating and cooling of thin films of D‐OPPE allows for a recrystallization from the melt, boosting the performance of D‐OPPE‐based transistors. The improved film properties induced by controlled annealing lead to a hole field‐effect mobility around 0.014 cm² V⁻¹ s⁻¹, an on/off ratio of 10⁶, a sub‐threshold swing of 3 V dec⁻¹ and a threshold voltage of −35 V, employing a poly(methyl methacrylate) (PMMA) gate dielectric. Thus, PFETs out of D‐OPPE compete now with spin‐coated, polycrystalline poly(3‐hexylthiophene)‐based PFETs.

     

Copper (II) as an Amperometric Indicator: Determination of Thorium

Abstract

It has been demonstrated that copper (II) is an attractive amperometric indicator for the titration of small amounts of thorium in solution. EDTA was used as the titrant. Best results are obtained in the titration when the mole ratio of thorium to copper is high. The method should be applicable to several other metal ions that form more stable EDTA complexes than does copper.     

A New Dimeric Copper(II) Complex of Hexyl Bis(pyrazolyl)acetate Ligand as an Efficient Catalyst for Allylic Oxidations

A new dimeric copper(II) bromide complex, [Cu(L^OHex)Br(μ-Br)]₂ (1), was prepared by a reaction of CuBr₂ with the hexyl bis(pyrazol-1-yl)acetate ligand (L^OHex) in acetonitrile solution and fully characterized in the solid state and in solution. The crystal structure of 1 was also determined: the complex is interlinked by two bridging bromide ligands and possesses terminal bromide ligands on each copper atom. The two pyrazolyl ligands in 1 coordinate with the nitrogen atoms to complete the Cu coordination sphere, resulting in a five-coordinated geometry—away from idealized trigonal bipyramidal and square pyramidal geometries—which can better be described as distorted square pyramidal, as measured by the τ and χ structural parameters. The pendant hexyloxy chain is disordered over two arrangements, with final site occupancies refined to 0.705 and 0.295. The newly synthesized complex was evaluated as a catalyst in copper-catalyzed C–H oxidation for allylic functionalization through a Kharasch–Sosnovsky reaction without any external reducing agent. Using 0.5 mol% of this catalyst, and tert-butyl peroxybenzoate (Luperox) as an oxidant, allylic benzoates were obtained with up to 90% yield. The general reaction time was only slightly decreased to 24 h but a very significant decrease in the alkene:Luperox ratio to 3:1 was achieved. These factors show relevant improvements with respect to classical Kharasch–Sosnovsky reactions in terms of rate and amount of reagents. The present study highlights the potential of copper(II) complexes containing functionalized bis(pyrazol-1-yl)acetate ligands as efficient catalysts for allylic oxidations.     

Nitrogen‐Doped Carbon Nanotube‐Based Bilayer Thin Film as Transparent Counter Electrode for Dye‐Sensitized Solar Cells (DSSCs)

Carbon nanotubes (CNTs) have been widely considered as one of the promising candidates for replacing fluorine‐doped tin oxide (FTO)/platinum (Pt) electrodes to reduce the fabrication cost of dye‐sensitized solar cells (DSSCs). Here, we report that a bilayer transparent film containing N‐doped CNTs (which are highly catalytic) and normal CNTs (which are highly conductive) as a counter electrode in DSSCs results in efficiencies up to 2.18 %, yet still maintains a good transparency with a transmittance of approximately 57 % at 550 nm.     

Deposition and Characterization of Luminescent Eu(tta)3phen‐Doped Parylene‐Based Thin‐Film Materials

Herein, novel host–guest films produced by coarse vacuum cosublimation of the parylene C dimer and Eu(tta)₃phen are prepared and studied. Eu(tta)₃phen sublimation at different temperatures allows films with different concentrations of the Eu complex to be obtained. The films are characterized by Rutherford backscattering spectrometry (RBS), FTIR spectroscopy, X‐ray diffraction (XRD), atomic force microscopy (AFM), and UV/Vis absorption and emission spectroscopy. RBS, FTIR, and XRD reveal the incorporation of Eu(tta)₃phen into the parylene matrix. AFM evidences the very flat film surface, which is particularly advantageous for optical applications. UV/Vis absorption and emission analyses confirm that the optical properties of Eu(tta)₃phen are preserved in the deposited films. Fluorescence measurements evidence the occurrence of an energy‐transfer process between parylene and Eu(tta)₃phen, and this results in an increase in the light emitted by the Eu complex that is as much as five times higher than that emitted by Eu(tta)₃phen alone.     

单斜层状结构锂离子电池正极材料LiY_xMn_(1-x)O_2的合成及其电化学性能

以Na2CO3、(CH3CO2)2Mn.4H2O、Y2O3和CH3COOLi.2H2O为原料,采用高温固相法经过2次灼烧和水热离子交换法得到一系列钇掺杂的LiMn1-xYxO2(x:0.01,0.02,0.03,0.05)化合物。通过XRD、XPS、循环伏安及恒电流充放电测试技术,研究了钇掺杂离子对合成正极材料结构及电化学性能的影响。结果表明,所得产物均具有单斜层状结构。合适的钇掺杂可以起到扩展锂离子脱嵌通道和稳定骨架结构的作用,钇离子的引入部分取代原有的三价锰离子,由于钇离子的离子半径较三价锰离子大,因此稀土掺杂锰酸锂材料的晶胞参数比未掺杂材料大,在一定程度上扩充了锂离子迁移的三维通道,更有利于锂离子的嵌入与脱嵌,提高单斜层状LiMnO2材料的电化学循环可逆性及循环稳定性。通过对所得化合物进行了钇掺杂量及电化学性能的研究,得到性能比较优良的LiY0.021Mn0.979O2化合物,其首次放电比容量为125.7mA.h/g,100次循环以后,放电比容量达212.1mA.h/g,远高于未掺杂材料的放电容量138mA.h/g。交流阻抗测试结果表明,Y3+的掺入能降低材料的电化学反应阻抗和提高材料中Li+的扩散能力。     

Neutral Nickel(II) and Copper(II) Tetraazamacrocyclic Complexes as Molecular Rods Attached to Gold Electrodes

New dithiolated derivatives of neutral Cu^II and Ni^II tetraazamacrocyclic complexes have been synthesized and characterized by spectroscopic and diffractional methods. These rod‐shaped molecules were assembled in monocomponent and mixed monolayers on gold electrodes. In the mixed monolayers, the active molecules were embedded in a hexanethiol matrix. The dithiolated complexes are oriented perpendicularly to the electrode, and reveal faster kinetics of electron transfer than those assembled in a single‐component monolayer. They appear as protrusions, which are easily addressed by using the STM method. In the presence of a suitable electron acceptor in the solution, the donor properties of the anchored Cu complex were weakened, which revealed donor–acceptor interactions with the monolayer. The peak position in the voltammogram indicates a stronger interaction of the solution‐based acceptor with the reduced Cu^II form than with the Cu^III complex. This suggests the possibility of switching the association on or off by applying an appropriate potential.