铁卟啉/钒取代杂多酸新型催化剂的合成、表征和性能研究

文章以水溶性碘化四对(4-三甲氨基苯基)铁卟啉和钒取代杂多酸H5PMo10V2O40为原料,采用离子交换方法在水溶液中合成了一种铁卟啉/钒取代杂多酸新型无机-有机复合催化剂,并使用红外和紫外光谱技术对其结构进行了表征,结果表明,这种新型复合催化剂仍然保持着卟啉的大环共轭结构和杂多酸的笼状多电子结构。同时研究了以30%过氧化氢水溶液为绿色氧化剂,初步探讨了这种铁卟啉杂多酸催化剂对苯的羟基化反应的的影响,考察了催化剂的催化活性。催化氧化实验表明,制备的铁卟啉/杂多酸配合物可用作苯直接氧化羟基化成苯酚的催化剂,并且表现出较高的催化活性。     

原位氧化Zn3N2制备P型ZnO薄膜的性能研究

采用射频反应溅射法在玻璃衬底上制备Zn3N2薄膜,然后向真空室中通入纯氧气进行热氧化制备ZnO薄膜.利用X射线衍射、扫描电子显微镜、霍尔效应测量、透射光谱和光致发光光谱等表征技术,研究了氧化温度和氧化时间对ZnO薄膜的结晶质量、电学性质和光学性能的影响.研究结果显示,450℃下氧化2h后的样品中除含有ZnO外,还有Zn3N2成分,500℃下氧化2h可以制备出电阻率为0.7Ωcm,空穴载流子浓度为1017cm-3,空穴迁移率为0.9cm2/Vs的具有c轴择优取向的p型ZnO薄膜.此时的ZnO薄膜具有良好的光学特性,紫外可见光范围内透过率为85%,处于紫外区域的激子复合产生的发光峰很强,且半高宽较窄,而处于可见光部分来自于深能级发射的绿色发光峰很弱.这种工艺制备的ZnO薄膜质量较好,有利于实现在短波长光电器件方面的应用.     

Effect of Li2O and CoO-doping of CuO/Fe2O3 system on its surface and catalytic properties

Physicochemical, surface and catalytic properties of pure and doped CuO/Fe₂O₃ system were investigated using X-ray diffraction (XRD), energy dispersive X-ray analysis (EDX), nitrogen adsorption at −196 °C and CO-oxidation by O₂ at 80-220 °C using a static method. The dopants were Li₂O (2.5 mol%) and CoO (2.5 and 5 mol%). The results revealed that the increase in precalcination temperature from 400 to 600 °C and Li₂O-doping of CuO/Fe₂O₃ system enhanced CuFe₂O₄ formation. However, heating both pure and doped solids at 600 °C did not lead to complete conversion of reacting oxides into CuFe₂O₄. The promotion effect of Li₂O dopant was attributed to dissolution of some of dopant ions in the lattices of CuO and Fe₂O₃ with subsequent increase in the mobility of reacting cations. CoO-doping led also to the formation of mixed ferrite Co_xCu_1−xFe₂O₄. The doping process of the system investigated decreased to a large extent the crystallite size of unreacted portion of Fe₂O₃ in mixed solids calcined at 600 °C. This process led to a significant increase in the S_BET of the treated solids. Doping CuO/Fe₂O₃ system with either Li₂O or CoO, followed by calcination at 400 and 600 °C decreased its catalytic activity in CO-oxidation by O₂. However, the activation energy of the catalyzed reaction was not much affected by doping.     

Ag‐doped TiO2 enhanced photocatalytic oxidation of 1,2‐cyclohexanediol

The superiority of silver‐doped titania for photocatalytic oxidation (PCO) of organic compounds inspired us to investigate PCO of 1,2‐cyclohexanediol. Ag/TiO₂ was prepared, characterized (nanosize 19–24 nm) and used for oxidation of 1,2‐cyclohexanediol (1) in acetonitrile. The photolysate was analyzed using GC and GC/MS techniques. The PCO products are 2‐hydroxylcyclohexanone (2), 1,2‐cyclohexandione (3), 2‐cyclohexenone(4), cyclohexanone (5), and adipic acid (6).The formation of electron–hole pair at the surface of the catalyst followed by oxidation reactions was the suggested mechanism. Kinetic studies revealed first‐order mechanism for PCO of 1 and rate constant (k) = ?0.145 h^–1. Copyright © 2012 John Wiley & Sons, Ltd.     

激光熔覆原位合成Nb(C,N)陶瓷颗粒增强铁基金属涂层

采用预涂粉末激光熔覆技术,在42CrMo基体上制备出原位合成Nb(C, N)颗粒增强的铁基复合涂层。X射线及扫描电镜分析结果表明：激光熔覆获得的涂层基体为耐氧化、耐蚀性良好的Fe-Cr细晶组织及少量的-Fe相,原位合成的Nb（C, N）呈块状弥散分布在基体上。进一步的磨损试验表明：这些颗粒增强相极大增强了抗磨损性能,与未熔覆的母材相比,其磨损失重仅为母材的1/9左右; 涂层在750 ℃恒温氧化条件下具有较好的抗氧化性能,氧化层主要由NbO1.1,Cr2O3相组成; 母材的氧化产物为Fe2O3,容易脱落,保护性能较差; 激光熔覆涂层的氧化膜厚度仅为未涂层的1/5。     

Effect of current density on the microstructure and corrosion behaviour of plasma electrolytic oxidation treated AM50 magnesium alloy

Plasma electrolytic oxidation (PEO) of an AM50 magnesium alloy was accomplished in a silicate-based electrolyte using a DC power source. Coatings were produced at three current densities, i.e. 15 mA cm⁻², 75 mA cm⁻², and 150 mA cm⁻² and were characterised for thickness, roughness, microstructural morphology, phase composition, and corrosion resistance. Even though the 15 min treated coatings produced at higher current density levels were thicker, they showed poor corrosion resistance when compared to that of the coatings obtained at 15 mA cm⁻². Short-term treatments (2 min and 5 min) at 150 mA cm⁻² yielded coatings of thickness and corrosion resistance comparable to that of the low current density coatings. The superior corrosion resistance of the low thickness coatings is attributed to the better pore morphology and compactness of the layer.     

Ultrasonic-assisted synthesis of Pd–Pt/carbon nanotubes nanocomposites for enhanced electro-oxidation of ethanol and methanol in alkaline medium

Herein, a facile ultrasonic-assisted strategy was proposed to fabricate the Pd–Pt alloy/multi-walled carbon nanotubes (Pd–Pt/CNTs) nanocomposites. A good number of Pd–Pt alloy nanoparticles with an average of 3.4 ± 0.5 nm were supported on sidewalls of CNTs with uniform distribution. The composition of the Pd–Pt/CNTs nanocomposites could also be easily controlled, which provided a possible approach for the preparation of other architectures with anticipated properties. The Pd–Pt/CNTs nanocomposites were extensively studied by electron microscopy, induced coupled plasma atomic emission spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy, and applied for the ethanol and methanol electro-oxidation reaction in alkaline medium. The electrochemical results indicated that the nanocomposites had better electrocatalytic activities and stabilities, showing promising applications for fuel cells.     

贮氢钛膜氢含量的中子反射分析方法设计

对3 μm厚Ti膜的中子反射率谱进行理论计算,得到了Ti膜在不同含氘量(TiDc,c=0.5、1.0、1.5和2.0)、表面是否氧化下的反射率谱.数据表明,用中子反射技术可以获取含氘量和表面氧化程度等信息.同时,根据需测量的膜层最大厚度,对反射谱仪部分参数提出了要求.     

Characteristics of selective oxidation during the fabrication of vertical cavity surface emitting laser

Taking into account oxidation temperature, N₂ carrier gas flow, and the geometry of the mesa structures this paper investigates the characteristics of selective oxidation during the fabrication of the vertical cavity surface emitting laser (VCSEL) in detail. Results show that the selective oxidation follows a law which differs from any reported in the literature. Below 435℃ selective oxidation of Al_0.98Ga_0.02As follows a linear growth law for the two mesa structures employed in VCSEL. Above 435℃ approximately increasing parabolic growth is found, which is influenced by the geometry of the mesa structures. Theoretical analysis on the difference between the two structures for the initial oxidation has been performed, which demonstrates that the geometry of the mesa structures does influence on the growth rate of oxide at higher temperatures.     

场发射栅孔阵列的制备

 采用硅的局部氧化技术以及湿法刻蚀技术,利用2.6 μm的光刻掩模板在n型硅片上形成了栅极孔径为1 μm的场发射阴极的栅极空腔阵列,实现了用大阵点尺寸的栅极掩模板制备较小尺寸栅孔阵列。硅的湿法刻蚀溶液采用各向同性的硝酸和氢氟酸混合溶液,刻蚀后空腔的深度和宽度均随刻蚀时间线性增加。同时,由于刻蚀溶液具有较高的Si/SiO₂ 刻蚀选择比,栅极孔径随刻蚀时间增大的速度远低于深度和宽度增大的速度,栅极孔径主要取决于掩模的尺寸和氧化层的厚度。通过选择掩模板的尺寸以及氧化层的厚度,采用局部氧化技术和湿法刻蚀技术能够制备出微米或亚微米的场发射阴极的栅极空腔阵列。