Er3+单掺、Er3+/Yb3+共掺杂Ca12Al14O32F2的 制备及上转换发光性质

利用高温固相法成功制备了Er~(3+)单掺、Er~(3+)/Yb~(3+)共掺杂Ca_(12)Al_(14)O_(32)F_2上转换发光样品。在980 nm激光激发下,Er~(3+)单掺和Er~(3+)/Yb~(3+)共掺杂样品均呈现出较强的绿光(528,549 nm)和较弱的红光(655 nm)发射,分别归因于Er~(3+)离子的~2H_(11/2),~4S_(3/2)→~4I_(15/2)和~4F_(9/2)→~4I_(15/2)能级跃迁。随着Er离子浓度的增加,单掺杂样品上转换发光强度先增大后减小,最佳掺杂浓度为0.8%。共掺杂Yb~(3+)后,Er~(3+)的发光强度明显增大。还原气氛下合成的样品上转换发光强度增大约两倍,可能和笼中阴离子基团变化有关。发光强度和激发光功率的关系表明所得上转换发射为双光子吸收过程,借助Er~(3+)-Yb~(3+)体系能级结构详细讨论了上转换发射的跃迁机制。     

Study on the mechanism of catalytic synthesis of dimethyldichlorosilane by AlCl3/MIL‐53(Al)@γ‐Al2O3

Dimethyldichlorosilane, one of the most consumed organosilicon monomers in the industry, can be prepared in a highly efficient and environmentally friendly synthesis method of disproportionating methylchlorosilanes. However, the internal mechanism of the reaction remains unclear. In this paper, the mechanism catalyzed by AlCl₃/MIL‐53(Al) and AlCl₃/MIL‐53(Al)@γ‐Al₂O₃ catalysts was calculated at B3LYP/6‐311++G(3df, 2pd) level by using the density functional theory (DFT). The results showed that although the two catalysts had similar active structures, the catalytic effects were significantly different. The Lewis acid center on the surface of γ‐Al₂O₃ in the core‐shell catalyst is complementary to the classic Lewis acid AlCl₃ through the spatial superposition effect, which greatly improves the Lewis acid catalytic activity of AlCl₃/MIL‐53(Al)@γ‐Al₂O₃.     

Surface passivation in n-type silicon and its application in silicon drift detector

Based on the surface passivation of n-type silicon in a silicon drift detector(SDD), we propose a new passivation structure of SiO2/Al2O3/SiO2 passivation stacks. Since the SiO2 formed by the nitric-acid-oxidation-of-silicon(NAOS)method has good compactness and simple process, the first layer film is formed by the NAOS method. The Al2O3 film is also introduced into the passivation stacks owing to exceptional advantages such as good interface characteristic and simple process. In addition, for requirements of thickness and deposition temperature, the third layer of the SiO2 film is deposited by plasma enhanced chemical vapor deposition(PECVD). The deposition of the SiO2 film by PECVD is a low-temperature process and has a high deposition rate, which causes little damage to the device and makes the SiO2 film very suitable for serving as the third passivation layer. The passivation approach of stacks can saturate dangling bonds at the interface between stacks and the silicon substrate, and provide positive charge to optimize the field passivation of the n-type substrate.The passivation method ultimately achieves a good combination of chemical and field passivations. Experimental results show that with the passivation structure of SiO2/Al2O3/SiO2, the final minority carrier lifetime reaches 5223 μs at injection of 5×10¹⁵ cm^-3. When it is applied to the passivation of SDD, the leakage current is reduced to the order of nA.     

Facile synthesis,characterization, and decolorization activity of Mn2+ and Al3+ co-doped hexagonal-like ZnO nanostructures as photocatalysts

A good photocatalyst with high efficiency can be synthesized easily using eco-friendly materials and processes. Our synthesized samples exhibit all of the aforementioned features. In this work, manganese co-doped ZnO at different weight percentages (3, 6, 9, and 15 wt.%) with and without 1.5 wt.% aluminum was synthesized by hydrothermal method, and their photocatalytic activity in aqueous solutions of methyl orange (MO) was investigated under visible light. The structural and optical properties of the samples were characterized using X-ray powder diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray analysis, and diffuse reflectance spectroscopy. In this work, Mn²⁺ ions in the 9%Mn/ZnO sample and Mn²⁺, Al³⁺ ions in the (9%Mn, 1.5%Al)/ZnO sample calcined at 800 °C were replaced instead with some Zn²⁺ ions in hexagonal wurtzite structures of ZnO. These structures were found next to each other in the form of a hexagonal shape that created 3D-hexagonal-like ZnO nanostructures. Finally, nanoparticles (NPs) and nano hexagonal-like ZnO nanostructures were, respectively, dispersed on the surface of 3D-hexagonal-like structure of 9%Mn/ZnO and (9%Mn, 1.5%Al)/ZnO. Diffuse reflectance spectroscopy analysis showed that the (9%Mn, 1.5%Al)/ZnO sample had more light absorption than 9%Mn/ZnO. However, contrary to our expectations, the 9%Mn/ZnO sample had better decolorization efficiency (94%) after 60 min under visible light, which could be attributed to a significant increase in the level of recombination by the aluminum ions.     

固体核磁共振结合密度泛函理论计算研究SSZ-39分子筛的钠离子落位与铝分布

具有AEI结构的SSZ-39分子筛的骨架外阳离子落位和铝分布对其催化性能影响显著.AEI笼中有三个结晶学不等价位，且铝取代T位具有一定的倾向性.本文结合固体核磁共振（NMR）技术（²⁷Al/²³Na MQ MAS NMR），以及密度泛函理论（DFT）计算，研究了不同硅铝比Na-SSZ-39分子筛中的Na⁺落位和铝分布.在孤立铝分布的情况下，铝原子优先占据于T3位，Na⁺主要落位于AEI笼中的SIIa0和SIII'a0位点上，其中SIII'a0位点的优先度较高，此外少部分Na⁺还落位于六棱柱内部的SIa0.当铝对存在时，AlSiSiAl分布的铝对占据六元环的对位（T3-T3），对应的Na⁺分别落位于SIIa1和SⅢ'a1位点.随着分子筛结构的部分破坏，游离的Na⁺可能形成明显的SIII'b位点.本文可加深对SSZ-39分子筛构效关系的理解，为更好地调控催化性能奠定基础.     

Manipulating OH−-Mediated Anode-Cathode Cross-Communication Toward Long-Life Aqueous Zinc-Vanadium Batteries

The anode-cathode interplay is an important but rarely considered factor that initiates the degradation of aqueous zinc ion batteries (AZIBs). Herein, to address the limited cyclability issue of V-based AZIBs, Al₂(SO₄)₃ is proposed as decent electrolyte additive to manipulate OH⁻-mediated cross-communication between Zn anode and NaV₃O₈ ⋅ 1.5H₂O (NVO) cathode. The hydrolysis of Al³⁺ creates a pH≈0.9 strong acidic environment, which unexpectedly prolongs the anode lifespan from 200 to 1000 h. Such impressive improvement is assigned to the alleviation of interfacial OH⁻ accumulation by Al³⁺ adsorption and solid electrolyte interphase formation. Accordingly, the strongly acidified electrolyte, associated with the sedated crossover of anodic OH⁻ toward NVO, remarkably mitigate its undesired dissolution and phase transition. The interrupted OH⁻-mediated communication between the two electrodes endows Zn||NVO batteries with superb cycling stability, at both low and high scan rates.     

X射线荧光光谱法快速测定铜基催化剂中金属含量

本文使用X射线荧光光谱仪,采用人工制备标样,以粉末直接压片和经验系数校正基体效应的方法,建立了铜基催化剂中CuO、ZnO和Al2O3含量的快速测定方法。考察了样品厚度的影响及方法的精密度和准确度。该法待测元素线性范围较宽,分别为:CuO:13.0%~97.0%,ZnO:0~63.0%,Al2O3:0~25.0%,且相关系数均大于0.99。测定各元素的相对标准偏差均小于0.3%,且测定结果与化学滴定分析结果吻合。该方法快速、简便,可应用于工业生产质量监控。     

双功能[Sn,Al]-Beta分子筛一步催化葡萄糖生成5-羟甲基糠醛

以部分脱铝的Beta分子筛为母体,采用同晶置换法将Sn植入骨架制备双功能[Sn,Al]-Beta分子筛,并应用于葡萄糖一步催化生成5-羟甲基糠醛(5-HMF)反应中.样品中Sn与Al的含量通过酸洗的浓度和酸洗的时间以及SnCl4处理的时间来控制.由于骨架中有与Al相关为B酸位,和Sn相关的L酸位,[Sn,Al]-Beta可作为一种双功能的固体酸催化剂.优化了[Sn,Al]-Beta催化葡萄糖一步催化生成5-HMF的反应参数,在最优Sn/Al比条件下,葡萄糖转化率为60.0%,5-HMF选择性为62.1%.     

CoFe2O4 nano-particles functionalized with 8-hydroxyquinoline for dispersive solid-phase micro-extraction and direct fluorometric monitoring of aluminum in human serum and water samples

A simple dispersive solid-phase micro-extraction method based on CoFe₂O₄ nano-particles (NPs) functionalized with 8-hydroxyquinoline (8-HQ) with the aid of sodium dodecyl sulfate (SDS) was developed for separation of Al(III) ions from aqueous solutions. Al(III) ions are separated at pH 7 via complex formation with 8-HQ using the functionalized CoFe₂O₄ nano-particles sol solution as a dispersed solid-phase extractor. The separated analyte is directly quantified by a spectrofluorometric method at 370 nm excitation and 506 nm emission wavelengths. A comparison of the fluorescence of Al(III)–8-HQ complex in bulk solution and that of Al(III) ion interacted with 8-HQ/SDS/CoFe₂O₄ NPs revealed a nearly 5-fold improvement in intensity. The experimental factors influencing the separation and in situ monitoring of the analyte were optimized. Under these conditions, the calibration graph was linear in the range of 0.1–300 ng mL⁻¹ with a correlation coefficient of 0.9986. The limit of detection and limit of quantification were 0.03 ng mL⁻¹ and 0.10 ng mL⁻¹, respectively. The inter-day and intra-day relative standard deviations for six replicate determinations of 150 ng mL⁻¹ Al(III) ion were 2.8% and 1.7%, respectively. The method was successfully applied to direct determine Al(III) ion in various human serum and water samples.     

Effects of anodic oxidation on corrosion properties of Al coating by arc spraying in seawater

A layer of Al coatings was prepared on the S355 steel by arc spraying, which was conducted by anodic oxidation treatment; the morphologies, chemical element compositions and phases of Al coating, and anodic oxide layer were analyzed with field emission scanning electron microscope (FESEM), energy dispersive spectrometer (EDS) and X‐ray diffraction (XRD), respectively. The corrosion protections of Al coating before and after anodic oxidation were discussed with a seawater immersion test; the corrosion resistance mechanisms of Al coating and anodic oxide layer in the seawater were also investigated. The results show that the thickness of Al coating is about 300 µm by arc spraying, the sample surfaces become loose after seawater immersion corrosion and Cl^? and O^2? penetrate into the substrate from the cracks, destroying the binding properties of coating–substrate, and the coating fails. After anodic oxidation, the oxide layer is formed in the surface of Al coating with the thickness of about 30 µm; the corrosion products are mainly composed of Al(OH)₃, which barraged the holes caused by seawater corrosion. The corrosion cracks are formed during the corrosion, while the number and depth of cracks decrease obviously after anodic oxidation treatment. The corrosion of Al coating becomes the local corrosion after anodic oxidation treatment, and the grains are smaller, which are easily nucleated to form a new corrosion resistance layer. Copyright © 2015 John Wiley & Sons, Ltd.