气相贝克曼重排新型固体酸催化剂研究

己内酰胺是一种重要的有机化工原料。采用环己酮肟的气相Beckmann重排的方法制己内酰胺可以解决传统的液相工艺中存在的副产硫酸胺、腐蚀设备和污染环境等问题。本研究的目的是开发出适合环己酮肟的气相Beckmann重排的固体酸催化新工艺。 首先，本工作用同位素标记的方法研究了Beckmann重排在固体酸B2O3/γ-Al2O3和TS-1上的反应机理。同位素标记后的产品采用质谱测量。通过与H218O交换氧，发现环己酮肟与H218O的交换在B2O3/γ-Al2O3和TS-1只能进行到一定程度，这暗示固体酸上腈中间体的解离不如经典的机理完全。提出了解离度(α)的概念，其定义为解离了中间体腈与总中间体腈之比。通过拟合实验数据和同位素标记的产品的计算公式，获得了B2O3/γ-Al2O3和TS-1上α 值分别为0.199和0.806的结果。 其次，采用对氧化铝表面合适氟化的方法，对氟化的氧化铝的性能进行研究。发现氧化铝表面氟化可以改善Beckmann重排的性能。氧化铝表面氟化可以消除其表面碱性位，说明了催化剂表面碱性位不利于Beckmann重排。而完全氟化的氧化铝的选择性不如某些固体酸如负载B2O3和Silicalite-1，暗示着表面酸强度也影响催化剂的选择性。同时，我们对适合气相Beckmann重排的催化剂进行了简单的筛选。发现一种稀土焦磷酸盐有可能是适合此反应的催化剂。 再次，研究了稀土焦磷酸盐催化剂上气相Beckmann重排。通过对一些稀土磷酸进行XRD,FT-IR,NH3-TPD和水接触角等表征，发现这类催化剂上表面的弱酸位以及合适的表面疏水是它们具有较好性能的原因。 再次，对焦磷酸铈催化剂的合成以及反应氛围进行了优化。发现优化的反应氛围为催化剂在pH在3~4时沉淀，在500~550度焙烧，在~350度反应，载气~80ml/min，空速在0.43h-1时反应，能保持转化率在98％以上，选择性在70％以上，8小时不失活。 最后，采用P123作为模板剂合成了一种新型的中孔稀土磷酸盐，这种稀土磷酸盐具有无序的虫洞形结构。应用这种新型的中孔稀土磷酸盐于酚类甲醇氧烷基化获得了较好的结果。与不加表面活性剂的材料相比，这种中孔稀土磷酸盐在低温下具有更大的活性并且其选择性不受损失。认为这种中孔的形态对催化性能具有好的影响。

钙钛石型复合氧化物La_xSr_(1-x)M_yM'_(1-y)O_3(M, M' = Mn, Fe, Co)的固体物理化学性质和催化性能的研究

钙钛石型复合氧化物由于具有许多独特的物理化学性质，如多种类型的磁性和导电性、对多种物理和化学因素的敏感性、高温下的稳定性和结构的明确易调性等长期以来一直受到固体物理、固体化学和催化科技工作者重视，本文第一部分详细总结了文献中有关这类氧化物的结构、电子状态、电磁性质、表面吸附性能、稳定性以及反应机理和催化性能等方面的重要结果。第二部分为催化剂的制备和表征方法。第三部分针对文献中研究较少的B位取代钙钛石型氧化物，系统研究了系列化合物LaM_yM'_(1-y)O_a (M, M' = Mn, Fe, Co)的固体物理化学性质和对NH3和CO氧化反应的催化性能，讨论了它们之间的关系。1. 催化剂的制备、晶体结构与光谱性质。2. LaM_yM'_(1-y)O_3(M、M' = Mn、Fe、Co)r的氧化还原性质和稳定性。3. 过渡金属离子的状态及其之间的相互作用。4. 催化剂中氧的形态。5. 氨氧化性能与固体物化性质之间的关系。6. 一氧化碳氧化与固体物化性质之间的关系。

METAL-ORGANIC CHEMICAL-VAPOR-DEPOSITION GROWTH OF GAN

Single-crystal GaN films have been deposited on (01 (1) over bar 2) sapphire substrates using trimethylgallium (TMGa) and NH3 as sources. The morphological, crystalline, electrical and optical characterizations of GaN film are investigated. The carrier concentration ofundoped GaN increases with decreasing input NH3-to-TMGa molar flow ratio.

GaN生长速率的研究

采用在位监控方法研究了MOCVD系统中GaN材料的外延生长速率与NH3流量、TMGa流量、Ⅴ/Ⅲ比等生长参数的关系.GaN生长速率随NH3流量的提高先增加后减小,而随TMGa流量的增加线性的增加.在不同NH3流量的情况下,GaN生长速率随TMGa流量增加的速率不同.GaN的生长速率与Ⅴ/Ⅲ比没有直接的关系,而与NH3,TMGa等条件有关.实验结果表明,MOCVD系统中存在着较强的预反应.预反应的程度与TMGa的流量成正比.

Homoepitaxial Growth and Characterization of 4H-SiC Epilayers by Low-Pressure Hot-Wall Chemical Vapor Deposition

Horizontal air-cooled low-pressure hot-wall CVD (LP-HWCVD) system is developed to get highly qualitical 4H-SiC epilayers.Homoepitaxial growth of 4H-SiC on off-oriented Si-face (0001) 4H-SiC substrates is performed at 1500℃ with a pressure of 1.3×103Pa by using the step-controlled epitaxy.The growth rate is controlled to be about 1.0μm/h.The surface morphologies and structural and optical properties of 4H-SiC epilayers are characterized with Nomarski optical microscope,atomic force microscopy (AFM),X-ray diffraction,Raman scattering,and low temperature photoluminescence (LTPL).N-type 4H-SiC epilayers are obtained by in-situ doping of NH3 with the flow rate ranging from 0.1 to 3sccm.SiC p-n junctions are obtained on these epitaxial layers and their electrical and optical characteristics are presented.The obtained p-n junction diodes can be operated at the temperature up to 400℃,which provides a potential for high-temperature applications.

In situ doping of 3C-SiC grown on (0001) sapphire substrates by LPCVD

The heteroepitaxial growth of n-type and p-type 3C-SiC on (0001) sapphire substrates has been performed with a supply of SiH4+C2H4+H-2 system by introducing ammonia (NH3) and diborane (B2H6) precursors, respectively, into gas mixtures. Intentionally incorporated nitrogen impurity levels were affected by changing the Si/C ratio within the growth reactor. As an acceptor, boron can be added uniformly into the growing 3C-SiC epilayers. Nitrogen-doped 3C-SiC epilayers were n-type conduction, and boron-doped epilayers were p-type and probably heavily compensated.

包膜与添加抑制剂结合型尿素的控效机理

对尿素进行包膜是控制尿素溶出的有效措施，但尿素包膜不能控制尿素溶出后的土壤生物化学转化行为。为了既控制尿素的溶出行为又控制溶出后尿素的水解或水解生成NH4+的硝化过程，本研究利用流化床喷涂技术将脉酶抑制剂氢醒（HQ）和硝化抑制剂双氰胺（DCD）分别加入聚合物包膜尿素内。包膜层的化学组成和通透性抉定性地影响着尿素和抑制剂的溶出特征。尿素从聚合物包膜内溶出过程可分成4个阶段：滞后阶段、溶胀阶段、稳定阶段和衰退阶段。在土壤中，HQ和DCD从包膜内溶出的速度快于尿素。尿素和HQ的同时缓慢溶出使尿素的水解过程比较平缓，有效避免了尿素在土壤中迅速水解所造成的土壤NH4+-N激增和土壤pH剧烈增加现象，使尿素氮的NH3挥发损失大幅度降低。DCD和尿素的同时控制溶出减小了DCD淋失的可能性，延长并增强了DCD对土壤硝化作用的抑制效果，并显著降低了土壤NO3-的淋失。水稻盆栽试验、小麦一白菜复种微区试验和玉米田间小区试验的结果表明，包膜尿素中添加DCD表现出了较高的肥效。施用添加DCD的包膜尿素明显增加了土壤NH4+-N的供应，增加了作物的N累积吸收量，并且使白菜产量显著增加了31.3％（与尿素分施相比）。尽管在包膜尿素中添加HO明显降低了土壤NH3挥发损失的可能性，但施用添加HQ的包膜尿素处理仅获得了与尿素分施处理相当的作物生物性状、N累积吸收量和产量。

下辽宁省河平原稻田生态系统的NH_3挥发和N淋溶

在地处下辽河平原的中国科学院沈阳生态实验站潮棕壤上布置施N量分别为180、240和300kg·hm~(-2)，施P量分别为70、100和130kg·hm~(-2)的稻田田间试验。应用通气密闭室法和陶土渗滤管法，测定了稻田生态系统三个不同施肥期施用氮肥后的NH3挥发损失和N淋溶，结果表明：1．水稻生长季节施用氮肥后有明显NH3挥发，总挥发量为11.64kgN·hm~(-2)-34.01kgN·hm~(-2)，占施N量的4.66％-11.66％，主要发生在施用分孽肥后，每次NH3挥发高峰出现在施氮肥后的2-4d内。2．水分渗漏对NH3挥发损失有重要影响。田面积水条件下，NH3挥发损失量及其占施N量的比率都较大，不同施N处理间差异显著（P＜0.05），NH3挥发量随施N量增加而增加；田面不积水条件下，NH3挥发损失挥发量相对较小。3．氮肥用量、田面水NH4斗一浓度和田面水pH是影响NH3挥发重要因素；180kgN·hm~(-2)条件下，积水时不同P处理间NH3挥发差异不显著。4．水稻生长季节各次施用氮肥后，60cm和gocm深处渗漏液中NH4+-N含量都小于2mg·L~(-1)，各施氮肥处理与对照间差异不显著。但NO3-淋溶比较显著，多集中在3mgN·ul-15mgN·L~(-1)之间。NO3-的淋溶随施N量增加而增加。水分渗漏状况影响N03一在不同土层深度的累积，渗水越快NO3-淋溶深度越大。渗水快或者施N量高时NO3，淋溶浓度高于国际饮用水卫生标准10mgN·L~(-1)，已有污染浅层地下水的可能。5．施用基肥后灌水，NH_4~+、NO_3~-立即出现淋溶高峰，而两次追施氮肥的淋溶高峰出现在施肥后10d或更久；并且基肥时期的淋溶浓度也比较高。

利用含纤维素原料发酵产氢的研究

本文从新鲜大熊猫粪便和实验室保存的沼气发酵富集物中筛选得到 4 株厌氧纤维素分解菌B5、C3、D3-2、D4-1，利用这4 株菌预处理秸秆，然后将预处理后的秸秆用本实验室保存的厌氧产氢菌来发酵进行生物产氢。同时还比较研究了：○1 用1% H2SO4、25% NH3 · H2O和12% NaOH对秸秆进行化学预处理；○2 用厌氧纤维素分解菌对秸秆进行生物预处理；○3 化学与生物组合预处理对秸秆发酵生物产氢的影响。实验结果表明：12% NaOH和生物组合预处理后的秸秆发酵产氢效果最好，其产氢量为21.04 mL g-1，是未经预处理秸秆的75 倍；最高氢气浓度为57.3%，是未经预处理秸秆的96 倍；其产氢的最适pH 为4.5 ~ 6.0，最佳底物浓度为45 ~ 55 g L-1；其发酵过程中的挥发性脂肪酸（VFAs）以乙酸和丁酸为主。 本实验筛选到的 4 株厌氧纤维素分解菌株中，B5 和D4-1 在降解纤维素的同时还具有直接以纤维素为底物产氢的功能，因此本文分别对菌株B5 和D4-1 以及二者的组合菌株B5+D4-1 直接利用秸秆为基质发酵生物产氢做了初步探索研究。结果发现：组合菌株发酵产氢的效果以及对秸秆纤维素和半纤维素的降解率要比单菌株好。菌株B5+D4-1 发酵，秸秆的产氢量为11.4 mL g-1，分别是B5 和D4-1 单菌株的1.6 倍和3.1 倍；组合菌株B5+D4-1 发酵的最大氢气浓度为31.6%，分别是B5 和D4-1 单菌株的1.3 倍和2.4 倍。在发酵过程中，组合菌株B5+D4-1 对秸秆纤维素和半纤维素的最高降解率分别为35.0%和11.8%，分别是菌株B5 的1.2 倍和1.1 倍，是菌株D4-1的1.5 倍和1.3 倍。菌株B5，D4-1 以及组合菌株B5+D4-1 发酵过程产生的挥发性脂肪酸（VFAs）均以乙酸为主。菌株B5 单独发酵过程中只检测到乙酸和丁酸，菌株D4-1 单独发酵以及组合菌株B5+D4-1 发酵过程检测到有乙醇、乙酸和丁酸。 The fermentative bio-hydrogen production by anaerobic hydrogen bacteria preserved in our laboratory from the straw which had been pretreated by four anaerobic cellulolytic decomposition strains of B5, C3, D3-2, D4-1 which were isolated and screened from giant panda’s excrement and biogas fermentation enrichments conserved in our laboratory was studied. Besides, the impact of chemical(1% H2SO4、25% NH3·H2O and 12% NaOH), biological (cellulolytic strains of B5, C3, D3-2, D4-1) and chemical-biological combination pretreatment on bio-hydrogen production from straw by fermentation was also comparatively studied. The experiments showed that the best results of bio-hydrogen production were obtained from the straw with 12% NaOH-biological combination pretreatment method, its capability of bio-hydrogen production was 21.04 mL g-1, which was 75 times higher than the straw without pretreatment; the maximum concentration of H2 was 57.3%, which was 96 times higher than the straw without pretreatment; its optimum pH range was 4.5 ~ 6.0, and its optimum range of substrate concentration was 45 ~ 55 g L-1; In the process of fermentation, the main composition of VFAs were acetate and butyrate. Among the four strains of B5, C3, D3-2, D4-1, B5 and D4-1 have the function of hydrogen-producing by cellulose used as substrate when it decompose cellulose, so the preliminary exploration and research on fermentative bio-hydrogen production by B5, D4-1 and B5+D4-1 which directly used straw as substrate was carried out. The results showed that the combination strains of B5+D4-1 was strikingly better than either B5 or D4-1 strain in the fermentative hydrogen production. The hydrogen-production capability of B5+D4-1 was 11.4 mL g-1 which was respectively 1.6 times and 3.1times higher than B5 and D4-1; the maximum hydrogen concentration of B5+D4-1 was 31.6% which was respectively 1.3 times and 2.4 times higher than B5 and D4-1. In the process of fermentation, the maximum degradation rate of cellulose and hemicellulose in straw was respectively 35.0% and 11.8% by B5+D4-1, which was 1.2 times and 1.1 times higher than B5, and was 1.5 times and 1.3 times higher than D4-1 respectively. The Volatile Fattty Acids(VFAs) generated in the process of fermentation with strains of B5, D4-1 and B5+D4-1 were all mainly acetate. Acetate and butyrate were detected in the process of fermentation with B5, ethonal, acetate and butyrate were detected in the process of fermentation with D4-1 and B5+D4-1.