Ca-Mg-Al复合氧化物催化尿素与1,2-丙二醇制碳酸丙烯酯

采用共沉淀法制备了系列Ca-Mg-Al复合氧化物催化剂，通过对沉淀剂配比、沉淀液pH值及焙烧温度等制备条件的考察，得到以Na₂CO₃为沉淀剂、pH=9.5、850℃下焙烧4h制备的Ca-Mg-Al催化活性最高。在 n(PG)∶n(urea)=1.5∶1、反应温度为145℃、绝压20kPa、反应时间4h、催化剂用量为尿素质量的5%时，碳酸丙烯酯收率达到84.6%。采用XRF、XRD、NH₃-TPD、SEM及BET对催化剂的组成、晶型及酸性进行了表征，发现随着沉淀剂中Na₂CO₃的含量增加，催化剂中CaO∶MgO的比例增大，碳酸丙烯酯的收率亦升高；经850℃焙烧后，催化剂中存在CaO和MgO两种活性中心，起协同催化作用；随着焙烧温度由700℃升高到850℃，NH₃-TPD脱附曲线向低温方向偏移，且强酸中心NH₃脱附峰面积比由81.14%明显下降为0，中强酸中心NH₃脱附峰面积比由0增加到78.07%，而碳酸丙烯酯收率由68%增加到84.6%，这表明催化剂强酸性位的减少是催化活性增加的主要原因。     

超支化镍系催化剂构效关系及催化乙烯齐聚机理

采用1.0G超支化大分子（1.0G）、3-取代水杨醛和NiCl₂·6H₂O为原料，依次经席夫碱反应和络合反应合成了3种新型具有不同取代基位阻的超支化水杨醛亚胺配体及其镍系催化剂，利用红外光谱（FTIR）、核磁共振氢谱（¹H NMR）、紫外光谱（UV-vis）、电喷雾质谱（ESI-MS）及电感耦合等离子体质谱（ICP-MS）等方法对合成出产物的结构进行表征。考察了配体空间位阻、溶剂种类、助催化剂种类及反应条件对催化乙烯齐聚性能的影响。研究结果表明，配体空间位阻对催化乙烯齐聚性能有较大的影响，当以甲苯为溶剂、甲基铝氧烷（MAO）为助催化剂，在最佳反应条件下，超支化邻苯基水杨醛亚胺镍系催化剂催化乙烯齐聚的活性为2.81×10⁵g/(mol Ni·h)，对高碳烯烃（C₁₀₊）的选择性为34.28%。此外，在超支化水杨醛亚胺镍系催化剂催化性能评价的基础上，对其催化乙烯齐聚的机理进行研究。     

Optimization of Selective Epitaxial Growth of Silicon in LPCVD

Selective epitaxial growth (SEG) of silicon has attracted considerable attention for its good electrical properties and advantages in building microstructures in high‐density devices. However, SEG problems, such as an unclear process window, selectivity loss, and nonuniformity have often made application difficult. In our study, we derived processing diagrams for SEG from thermodynamics on gas‐phase reactions so that we could predict the SEG process zone for low pressure chemical vapor deposition. In addition, with the help of both the concept of the effective supersaturation ratio and three kinds of E‐beam patterns, we evaluated and controlled selectivity loss and nonuniformity in SEG, which is affected by the loading effect. To optimize the SEG process, we propose two practical methods: One deals with cleaning the wafer, and the other involves inserting dummy active patterns into the wide insulator to prevent the silicon from nucleating.     

多层薄膜结构气敏效应研究

在SnO2气敏薄膜层上覆盖一层或多层钝化材料（SiO2,Al2O3) 薄膜，制成的多层膜气敏元件，可很好地排除大分子气体如乙醇等对小分子H2检测的干扰，使其具有单独检测H2的功能。本文还通过测量元件的升温曲线，推导出敏感体表面的氧吸附活化能；找出活化能与灵敏度、选择性的关系。根据实验现象和物性分析结果，试着探讨了元件的敏感机理。     

Menke条件下甲苯的固体酸催化选择性硝化

在Ｍｅｎｋｅ条件下，固体酸能对硝酸盐硝化甲苯的位置选择性产生影响，在所选的几种固体酸中皂土和高岭土是较好的对位选择性硝化催化剂，能使硝化产物的对邻比率达１．１～１．５。     

含氮化合物废气选择性催化氧化技术研究进展

通过对当前含氮化合物废气治理技术的对比分析,总结选择性催化氧化的相关技术优势。根据对含氮化合物的种类及来源分析,介绍氨气、腈类、胺类及其他含氮化合物的催化净化技术。重点总结催化剂的种类、研发进展和在实际使用中可能遇到的问题,同时展望含氮化合物废气选择性催化氧化技术的研发方向。     

催化反应精馏制备乙酸乙酯

利用反应精馏装置研究了乙酸和乙醇直接酯化法合成乙酸乙酯的转化条件:加热温度200 ℃,浓硫酸质量占混和物总质量0.6%,回流比为3∶1,乙酸与乙醇的摩尔比为1.15∶1.以反应精馏方式进行时,乙醇转化率、乙酸乙酯收率分别为94.09%和60.45%,明显高于普通蒸馏法,而乙醇转化为乙酸乙酯的选择性变化不大.     

Selective and nonselective wet etching of Zn0.9Mg0.1O/ZnO

Wet etch rates at 25°C for Zn_0.9Mg_0.1O grown on sapphire substrates by pulsed laser deposition (PLD) were in the range 300–1100 nm · min⁻¹ with HCl/H₂O (5×10⁻³−2×10⁻² M) and 120–300 nm · min⁻¹ with H₃PO₄/H₂O (5×10⁻³−2×10⁻² M). Both of these dilute mixtures exhibited diffusion-limited etching, with thermal activation energies of 2–3 kCal · mol⁻¹. By sharp contrast, the etch rates for ZnO also grown on sapphire by PLD were much slower in similar solutions, with rates of 1.2–50 nm · min⁻¹ in HCl/H₂O (0.01–1.2 M) and 12–54 nm · min⁻¹ in H₃PO₄/H₂O (0.02–0.15 M). The etching was reaction limited over the temperature range 25–75°C, with activation energies close to 6 kCal · mol⁻¹. The resulting selectivity of Zn_0.9Mg_0.1O over ZnO can be a high as ∼400 with HCl and ∼30 with H₃PO₄.     

Synthesis of ZSM-5 zeolite membranes without organic templates using a varying-concentration technique

Template-free nanosized ZSM-5 seeds with an average size of 15 nm were prepared from a synthesis solution with the composition 12Na2O:100SiO2:2Al2O3:2500H2O. By the use of these seeds, thin ZSM-5 zeolite membranes were prepared on the outer surface of a porous α-alumina tube with a pore size of 2 μm in a gel system by varying-concentration synthesis with organic-free template. The first composition synthesis sol-gel was the same as seeds of molar composition and the second one was 12Na2O:100SiO2:2Al2O3:5000H2O at 180 ℃ for 10 h, respectively. XRD shows that the film consists of well-crystallized ZSM-5 zeolite. SEM investigation indicats that the zeolite films on the supports are defect free and the film thickness is approximately 8 μm. The permeances for H2, N2, CH4 and CO2 are 8.94×10-7 , 3.27×10-7 , 3.9×10-7 , 3.14×10-7 and 0.874×10-7 mol·m2·s-1·Pa-1 , respectively. The ideal selectivity of membrane at room temperature for H2/CO2, H2/N2, H2/CH4 are 2.84, 2.73 and 2.29, respectively.     

In situ FTIR spectroscopy on rhodium-exchanged NaX zeolite with different metal dispersion during syngas reaction

In situ FTIR spectroscopy has been applied to study the reason of the different selectivity behaviour of rhodium in the CO hydrogenation reaction in dependence on the different particle size. Several forms of molecularly adsorbed CO are observed, such as linearly- and bridgedbonded CO on metallic rhodium as well as dicarbonyl species with Rh(I) centres formed by oxidation of Rh(0) with protons in presence of CO. Furthermore, non-reactive formate, acetate, and carbonate species are produced as side products of the reaction. The higher selectivity to oxygenates, particularly to methanol, is explained by the existence of multiple-bonded CO present only on small rhodium crystallites. The multiple-bonded CO formed at low temperatures is converted at higher temperatures to the highly reactive formyl species, which is hydrogenated to methanol.