Cu，Pd－ZSM－5上NO分解和CO氧化的催化作用

双交换Ｃｕ，ｐｄ－ＺＳＭ－５催化剂（Ｃｕ交换度为１０５％，Ｐｄ交换度分别为３．４％和３３％）对ＣＯ氧化反应有活性增强作用，对ＮＯ分解反应不存在增强效应．双交换催化剂在于交换程序不同，而表面物种不同，活性组分的分布状态不同，因而有不同的活性．先交换Ｃｕ，４００℃焙烧后再交换ｐｄ的Ｃｕ－Ｐｄ－ＺＳＭ－５催化剂，对上述两类反应的活性存双组分催化剂中均为最高．Ｈ_２－ＴＰＲ谱表明，共交换的Ｃｕ－Ｐｄ－ＺＳＭ－５中尚有部分ＣｕＣｌ＋占据了部分交换位置，而使ＣＯ氧化活性稍有下降．Ｎ_２－ＤＴＡ和Ｈ_２－ＴＰＲ谱结果表明，Ｐｄ交换到Ｃｕ－ＺＳＭ－５中后，抑制了吸附水和水合铜化合物的形成，由此提高了在２００—３００℃时氧的吸附量．后者的大小和ＣＯ氧化活性有顺变关系．Ｎ_２－ＤＴＡ谱中３４０—４４５℃的放热峰可能分别表征了和ＮＯ分解活性有关的铜氧桥或把氧桥的形成，该放热峰的峰温愈低，峰面积愈大，则ＮＯ分解活性愈高．     

Cu－ZSM－5分子筛中铜的超计量交换和铜氧铜桥的形成

用离子选择性电极原位监测离子交换制备ＣＵ－ＺＳＭ－５的过程，并用ＴＰＤ－ＭＳ研究了样品加热脱水时的变化．发现在ｐＨ值较高的条件下铜可能多数以Ｃｕ（ＯＨ）＋参与交换而使Ｃｕ－ＺＳＭ－５达到所谓的超计量交换．当新鲜样品受热时，Ｃｕ（ＯＨ）＋会迁移至另一个Ｃｕ（ＯＨ）＋的近邻进行脱水而形成铜氧铜桥，此桥可进一步脱氧而使二价铜还原成一价铜．迁移、脱水形成铜氧铜桥的过程是完全可逆的．     

Cu－ZSM－5分子筛中铜的精细结构和NO催化分解

用ＥＸＡＦＳ技术研究了不同交换度的和还原、再氧化处理的Ｃｕ－ＺＳＭ－５分子筛中铜离子的精细结构．在ＺＳＭ－５分子筛中，存在两种铜可占据的位置：一种具有饱和的氧配位和较短的铜氧距离，另一种钢氧配位不饱和且铜氧距离较远．离子交换时，铜离子可能优先占据前者，其量低于３０％．这两类铜的催化能力差别甚大，前者几乎无催化分解ＮＯ的活性．     

NO在Cu－ZSM－5分子筛上程序升温脱附研究

本文用等温动态吸附和程序升温脱附技术研究了ＮＯ与Ｃｕ－ＺＳＭ－５的相互作用，并根据还原预处理样品上ＮＯ吸、脱附循环的研究探讨了全过程样品所经历的氧化还原循环，在２５℃等温吸附时，ＮＯ与Ｃｕ￣＋和／或Ｃｕ￣０反应产生了Ｎ＿２、Ｎ＿２Ｏ和Ｃｕ￣（２＋）以及超晶格氧，同时在Ｃｕ￣＋上有许多可逆吸附的ＮＯ．ＮＯ吸附在Ｃｕ￣（２＋）上是稳定的，升高温度时，ＮＯ分为三种状态脱附，分别位于约１００，１８０和４００℃．后两种可能以Ｃｕ￣（２＋）－ＮＯ＿２和Ｃｕ￣（２＋）－ＮＯ＿３为中间态．第三种ＮＯ脱附同时伴随着Ｏ＿２脱附，对于还原预处理的样品，吸附和脱附的一个循环总体上会使样品部分氧化。     

Cu－ZSM－5分子筛表面铜离子的价态研究

以吸附ＣＯ红外光谱结合ＴＰＲ谱详细表征了经真空自还原及用不同还原剂还原的ＣｕＺＳＭ－５分子筛样品，考察了表面铜离子的价态分布情况及其影响因素。得知铜在Ｃｕ－ＺＳＭ－５表面是分步还原的。用不同方法进行氧化和还原时的难易程度不同。研究了用不同方法进行氧化还原时铜的价态转变条件和铜离子在不同价态间氧化还原循环的可逆性。Ｃｕ２＋与Ｃｕ＋间的氧化还原循环完全可逆，而Ｃｕ０与Ｃｕ＋间的氧化还原循环不完全可逆。Ｃｕ０氧化为Ｃｕ＋比Ｃｕ＋氧化为Ｃｕ２＋容易进行，探讨了Ｃｕ＋在Ｃｕ－ＺＳＭ－５分子筛中不同位置的分布情况及铜在不同条件下的氧化还原机理。     

Cu-ZSM-5分子筛中铜的超计量交换和铜氧铜桥的形成

用离子选择性电极原位监测离子交换制备Ｃｕ－ＺＳＭ－５的过程，并用ＴＰＤ－ＭＳ研究了样品加热脱水时的变化，发现在ＰＨ值，较高的条件下铜可能多数以Ｃｕ（ＯＨ）＾＋参与交换而使Ｃｕ－ＺＳＭ－５达到所谓的超计量交换，当新鲜样品受热时，Ｃｕ（ＯＨ）＾＋会迁移到另一个Ｃｕ（ＯＨ）＾＋的近邻进行脱水而形成铜氧铜桥，此桥可进一步脱氧而使二价铜还原成一价铜，迁移，脱水形成铜氧铜桥的过程是完全可逆的。     

Cu-M/ZSM-S(M=Ce,La,Ag)催化剂的表征及其对NO直接分解催化活性的研究

考察了用分散法制备的Ｃｕ－Ｍ／ＺＳＭ－５（Ｍ＝Ｃｅ,Ｌａ,Ａｇ）催化剂对ＮＯ直接分解的催化活性,并且用ＸＲＤ、ＳＥＭ、ＴＰＲ、ＸＰＳ及ＩＣＡＰ等手段对催化剂进行了表征。结果表明添加Ｃｅ有利于增加催化剂的铜离子交换度,添加Ａｇ有可能使ＺＳＭ－５分子筛的骨架结构发生改变,从而对催化剂活性产生影响。     

A_2BO_4型催化活性材料结构与性能的研究Ⅰ．［La_（k－x）Sr_x□_（1－k）］_2Cu_（1－y）□_yO_（4－δ）体系

以硝酸盐为原料，用柠檬酸络合法按［Ｌａ１－ｋＳｒｘ□ｋ－ｘ］２ＣｕＯ４（Ｘ＝０、０．０５、０．１、０．１５、０．２，ｋ＝０．０２５）的配比制备了５个样品．应用多晶Ｘ射线衍射法研究了此Ｌａ－Ｓｒ－Ｃｕ－Ｏ系列Ａ２ＢＯ４型复合氧化物的非完整结构．结构研究表明，此系列结构空位型非完整的存在，使结构中Ｂ位的铜离子变价为Ｃｕ２＋和Ｃｕ３＋．但是，随着Ａ位Ｓｒ加入量的增加，Ａ位空位的减少，结构中Ｂ位Ｃｕ３＋量随之减少，Ｃｕ２＋量随之增加，样品对于ＣＯ氧化的催化性能缓慢下降，而ＮＯ还原的催化能力增强．高价态的Ｃｕ３＋的存在是实现对ＣＯ催化氧化的条件；而Ｃｕ２＋给电子能力促进了Ｎｏ－的生成，是ＮＯ催化还原的活性来源．从此系列样品的催化性能和精细结构的研究可得出，适当地调节Ａ２ＢＯ４型结构中Ａ位和Ｂ位的空位及Ｓｒ２＋的掺入量，使Ｂ位Ｃｕ２＋和Ｃｕ３＋保持适当的比例，可获得ＣＯ催化氧化和ＮＯｘ催化还原同时具有较高活性的催化活性材料．     

富氧条件下甲烷还原NOxCo—ZSM—5催化剂的性能和表征

利用不同浓度和不同ＰＨ值的交换溶液，制得一系列Ｃｏ－ＺＳＭ－５催化剂，对富氧条件下催化剂甲烷选择性还原ＮＯＸ的活性进行了测定，由实验结果得知，富氧时，催化剂上氧化氮还原活性和甲烷的选择性随反应温度的变化２，分别在４４０℃和４１０℃有一极大值，应用ＩＲ、ＴＰＲ、ＸＰＳ和ＴＰＤ－ＭＳ等技术对催化剂进行了表征，观察到Ｃｏ＾２＿在ＺＳＭ－５分子筛上有两种不同落位，在Ｃｏ＾２＋离子与ＺＳＭ－５分子筛中的Ｎａ     

分散法制备的CuCl／ZSM—5分子筛催化上C3H6选择性催化还原NO …

研究了由分散法制备的ＣｕＣｌ／ＺＳＭ－５分子筛催化剂上丙烯在过量氧存在下选择催化还原ＮＯ反应，发现该法能使活性组份高度分散于载体上，且所制备的高负载量ＣｕＣ；／Ｈ－ＺＳＭ－５与离子交换法制备的Ｃｕ－ＺＳＭ－５相比在较低反应温度下具有更高的反应活性。     

SYNTHESIS AND REACTIONS OF SOME 2-THIENYL- AND 2-THENOYL-DERIVATIVES OF THIAZOLE AND THIADIAZOLINE AND THEIR SELENIUM ANALOGS

Abstract

2-(Thiocyanatoacetyl)thiophene 2 and its selenium analog 3 couple with diazotized anilines and yield 3-aryl-2-imino-5-(2-thenoyl)-2,3-dihydro-1,3,4-thiadiazoles 6 and 3-aryl-2-imino-5-(2-thenoyl)-2,3-dihydro-1,3,4-selenadiazoles 7 respectively. The reactions of both 6 and 7 with nitrous acid, acetic anhydride and benzoyl chloride are described. Azo coupling of 2-amino-4-(2-thienyl)thiazole 17 and its selenazole analog 18 with diazotized anilines yielded the arylazo derivatives 19 and 20 respectively. Reaction of the hydrazidoyl bromide 16 with potassium thiocyanate, potassium selenocyanate, thiourea and selenourea yields 6, 7, 19, and 20 respectively.     

生物质热解、加氢热解及其与煤共热解的热重研究

在加压热天平上用非等温热重法进行生物质（锯末、稻壳）在Ｎ２气氛下的热解和加氢热解研究。考察了升温速率（５～２５℃／ｍｉｎ）和压力（０．１～７ＭＰａ）的影响，求取了热解动力学参数，并研究了生物质与煤在常压Ｎ２气下的共热解过程。研究结果表明：生物质在４００℃左右即完成热解反应，总失重率大于７０％（Ｗ％，ｄａｆ．），热解时仅一个峰位于３００℃左右；与煤热解行为相同，随升温速率及压力的升高，转化率下降，ＤＴＧ峰移向高温，但由于热解反应在较低温度下进行，氧气的存在对生物质热解ＴＧ和ＤＴＧ的影响远小于煤热解。证明生物质热解以其内部氢对自由基的饱和及分子重排反应为主。生物质热解可用一级反应动力学处理，主要热解阶段及表现活化能分别为：锯末，２６７～３１４℃，６９．６６ｋＪ／ｍｏｌ；稻壳，２８３～３１０℃，５３．４５ｋＪ／ｍｏｌ；生物质由于与煤的热分解温度相差很大，因而在其共热解过程中无协同作用。     

温度及pH敏感N-异丙基丙烯酰胺/β-环糊精水凝胶的合成与性能研究

用顺丁烯二酸酐 (MAH)对具有分子包结能力的 β 环糊精 (β CD)进行化学改性 ,合成出了丁烯二酸单酯化 β CD单体 (MAH β CD) .通过氧化还原自由基引发MAH β CD与N 异丙基丙烯酰胺 (NIPA)聚合 ,合成出含 β CD结构单元的新型水凝胶 .用核磁共振、红外光谱及元素分析对MAH β CD单体及共聚物的结构和组成进行了表征 .溶胀研究结果表明 ,该水凝胶具有较好的pH、温度及离子强度敏感性 ;并且水凝胶在较高羧基(—COOH)含量和弱碱环境中 ,仍能表现出明显的温敏性     

MECHANICS AND THE EVOLUTION AND FUNCTIONAL MORPHOLOGY OF CONCHOSTRACAN CARAPACE MECHANICS AND THE EVOLUTION AND FUNCTIONAL MORPHOLOGY OF CONCHOSTRACAN CARAPACE

Conchostracans, with a laterally compressed body enclosed between two symmetric valves, live swimming in fresh or brackish water. The carapace valve has a number of growth bands with various sculptures. The general trend of sculptural evolution is from smooth to punctate-minute polygon-medium reticulation-large reticulation, while these punctate, polygonal and various reticulate patterns may separately develop into various radial ridges. The development of sculpture can be well explained by mechanical principle. Functional morphology of carapace is discussed in the light of mechanics in this paper.     

SURFACE ENTHALPY AND ENTROPY AND THE PHYSICO-CHEMICAL NATURE OF HYDROPHOBIC AND HYDROPHILIC INTERACTIONS

The attractive Interactions between typically hydrophobic molecules such as hexane or CCl₄, and the repulsive Interactions between extremely hydrophilic molecules such as poly(ethylene oxide) (PEO), when immersed in water, as well as the interactions between these molecules and water, have been examined from a surface thermodynamic viewpoint, taking the changes in surface free energy into account, as a function of temperature. It was found that attractive hydrophobic Interactions are not, as vas generally believed up to now, invariably entropic. Hydrophobic Interactions can be mainly enthalpic or mainly entropic, or more or less equal mixtures of both, depending on each individual case; however, all hydrophobic interactions are polar (in the sense of Lewis acid-base) in nature. Repulsive hydrophilic interactions are enthalpic, and also polar in nature. The interaction between hydrophobic solutes and water is mainly enthalpic, and is apolar in nature.     

CHLOROPHYLL a AND CAROTENOID AGGREGATES AND ENERGY MIGRATION IN MONOLAYERS AND THIN FILMS

Abstract— The spectra of absorption, fluorescence and excitation of monolayers and thin films containing chlorophyll a together with a carotenoid (cis-β-carotene, trans-β-carotene, fucoxanthin, or zeaxanthin), were measured at — 196°C. The concentration ratios used, (Chl)/(Car), were 6:1, 4:1, 3:1, 2:1, 1:1 and 1:3, and the area densities, 3·70, 2·55, 1·76, 0·71, 0·37 and 0·17 nm²/pigment molecule. In dilute monolayers, (3·70 nm²/molecule), with a constant concentration ratio (Chl)/(Car) = 3:1, evidence of three β-carotene forms, with absorption bands at 460, 500 and 520 nm (C₄₆₀, C₅₀₀ and C₅₂₀), and of a chlorophyll a form with an absorption band at 669–672 (Chl_669–672) was found. On increasing the density to 0·2–0·3 nm²/molecule, a conversion of C₄₆₀ and C₅₂₀ into C₅₀₀, was observed, and several more additional (probably more strongly aggregated) chlorophyll a forms appeared, with absorption bands at 672–733 nm. With excess carotene [(Chi)/(Car) = 1:3] the forms C₄₆₀, C₅₀₀, C₅₂₀ and Chl_669–672 were present even in the most dense films (0·2–0·3 nm²/molecule). The same was found with other carotenoids: if one of the pigments was in excess, aggregated forms of the other tended to disappear. In the transfer of energy from carotenoids to chlorophyll a, C₅₀₀ was found to be the main donor. In layers with a concentration ratio (Chl)/(Car) = 3:1, the efficiency of transfer was less than 10 per cent at the lowest density used (3·70 nm²/molecule); it increased to 50 per cent, as the density was increased to 0·20 nm²/molecule. When the relative concentration of the carotenoid was increased to (Chl)/(Car) = 1:1, the efficiency of energy transfer dropped to 25 per cent even at 0·20 nm²/molecule. It seems that the efficiency of energy transfer between carotene molecules (prior to its transfer to chlorophyll a) is low, and effective transfer occurs only between β-carotene and immediately adjacent chlorophyll a molecules.     

聚壬酰胺的制备纺丝及结构与性能测定

9-氨基壬酸系从癸二酸经单酯化、氨化和Hofmann重排制得。该单体以10克规模在玻璃管中和以4公斤量在15升聚合釜中,于260℃聚合成聚壬酰胺。聚合物在288℃纺丝,120℃牵伸,得到尼龙-9纤维。测定了聚合物和纤维的结构和多种性能。     

四个酰基硫脲衍生物及其配合物的合成与表征

本文报道了四个Ｎ－酰基硫脲衍生物及其Ｃｕ＾２＋，Ｎｉ＾２＋，Ｃｄ＾２＋，Ｓｎ＾４＋配合物的合成。用质谱、红外光谱、紫外光谱对它们进行了结构、性质表征。配体与金属离子配位主要是通过硫原子进行，配合物都是非离子型的。     

PHOTOLYSIS AND RADIOLYSIS OF NITROMETHANE AND NITROETHANE

Abstract— Prolonged photolysis of nitromethane and nitroethane in liquid and vapour phases, with simultaneous photolysis of the nitrogen dioxide formed, was studied in the absence and presence of cupric oxide. A high-pressure quartz immersion lamp providing the full range of visible and u.v. spectrum, with a high output of radiation at 366 and 313 mμ, was employed as source of light. The products of photolysis were detected by microanalytical methods, infrared-absorption spectrum analysis and gas chromatography. Photolysis of liquid nitro-alkanes resulted in formation of many compounds; saturated hydrocarbons, and in the case of nitroethane, ethylene, were submitted to detailed examination. Photolysis in the vapour phase was carried out in a specially designed glass apparatus. The main products were nitrogen dioxide, aldehydes and polyaldehydes; hydrocarbons were not estimated.
Liquid nitromethane and nitroethane were also irradiated with γ-rays from a ⁶⁰Co source. The radiolysis products were similiar to those obtained on photolysis. The mechanism of photolytic decomposition of nitroalkanes is proposed and discussed.