小晶粒ZSM-5沸石的绿色、经济性合成（英文）

通过添加少量silicalite-1做为活性晶种在较宽的SiO_2/Al_2O_3比范围内制备得到了小晶粒ZSM-5沸石,对所得样品进行X射线衍射(XRD),扫描电子显微镜(SEM),透射电子显微镜(TEM),N_2吸附-脱附,氨程序升温脱附(NH3-TPD)以及吡啶吸附红外(Py-IR)表征。研究结果表明活性晶种能有效导向生成ZSM-5沸石,避免杂晶形成并可减小所得沸石的晶粒尺寸;所得ZSM-5在低硅铝比(SiO_2/Al_2O_3 ratio=30)时呈纳米颗粒聚集体形貌,具有多级孔道结构性质;在较高硅铝比时(SiO_2/Al_2O_3 ratio=60–120)呈小晶粒形貌,颗粒尺寸大约200 nm。值得注意的是由胶态晶种引入的少量TPAOH不完全堵塞沸石的微孔孔道,因此所得所有沸石均无需提前焙烧除去模板剂即可进行离子交换得到具有酸性的H型ZSM-5沸石,所得酸性H型ZSM-5沸石具有和常规方法得到的相同SiO_2/Al_2O_3比的ZSM-5相似的酸类型、强度和酸量,在催化甲醇转化制备烯烃时呈现出相似的甲醇转化率和烯烃选择性。与常规ZSM-5制备方法比较,该方法能够大大减少模板剂的使用量,避免了样品离子交换前的焙烧,方法绿色清洁、成本低廉,具有很好的潜在的工业应用前景。     

合成高硅铝比的ZSM-5沸石的新过程

ZSM-5沸石是美国Mobil公司最早在(TAA)__2O—Na_2—Al_2O_3—SiO_2—H_2O体系中合成的,其SiO_2/Al_2O_3比可在相当大的范围内变化。1977年美国联合碳化物公司从上述体系不加铝合成了纯硅沸石,称做“Silicalite”,具有与ZSM-5沸石相同的骨架结构,被认为是ZSM-5沸石系列的最后一个成员.由于它基本上不含铝和基本上没有阳离子位置,所以显示有高度的亲有机物和疏水特征,能够将有机物从水中分离出来.     

阳离子(K~+、Na~+)对非水体系合成ZSM-48沸石性能的影响

研究了在非水体系(双胺体系)中KZSM-48和NaZSM-48沸石的晶化过程,发现NaZSM-48的晶化速度明显较KZSM-48为快。通过SEM、IR和TG-DTA的测定,发现K~+、Na~+离子对非水体系合成的ZSM-48沸石物性有较大的影响。晶化过程中在液相未检出SiO_2和Al_2O_3,表明在非水体系中ZSM-48沸石的生成属于固相转化。并且随着SiO_2/Al_2O_3比的增加,KZSM-48的晶粒粒径增大。通过CO+H_2生成烯烃反应可以看出NaZSM-48较KZSM-48有较高的活性和烯烃选择性。     

CoSAPO-34分子筛的合成、表征及其光催化脱氮性能

利用水热合成法,以三乙烯四胺(TETA)为模板剂,正硅酸乙酯、磷酸、氢氧化铝及乙酸钴为原料,合成了CoSAPO-34分子筛。通过扫描电子显微镜(SEM)、粉末X射线衍射(XRD)、热重(TG)、N2吸附-脱附和紫外-可见漫反射光谱(UV-Vis DRS)等方法对合成的分子筛进行表征。以吡啶-正辛烷体系为模拟油品对分子筛催化剂的脱氮效果进行评价,考察了样品的用量、光催化时间及循环催化次数对其脱氮性能的影响。结果表明:当合成原料的物质的量之比为n_(P_2O_5)∶n_(Al_2O_3)∶n_(SiO_2)∶n_(Co)∶n_(TETA)=1∶0.82∶0.26∶0.81∶2.05,在200℃晶化24 h,合成得到粒径约为50μm、仍保持了SAPO-34分子筛的骨架结构、形貌为立方体的Co SAPO-34分子筛,而且该分子筛具有较好的热稳定性。在500 W氙灯光照条件下反应150 min,样品对质量分数为100μg·g-1模拟油品的脱除率达到70%,循环3次光催化脱氮活性基本保持不变。     

莫来石管上丝光沸石膜的合成与渗透汽化性能

采用不添加有机模板剂、配比为n_(Na_2O):n_(Al_2O_3):n_(SiO_3):n_(H_2O)=0.25:0.015～0.1:1:15～60溶胶,在涂有晶种的多孔莫来石管上水热合成出了丝光沸石膜。制备的膜经XRD和SEM表征。考察了合成时间、硅铝比、水硅比和硅源等因素对膜生长及其性能的影响。合成时间的延长有利于丝光沸石c轴方向的优先生长,然而优先取向生长膜层并未提高膜在水/乙醇分离体系中的渗透通量和选择性。优化条件下合成的膜具有较高的渗透汽化性能,在348 K、水/乙醇(10/90,W/W)混合溶液中的渗透通量和分离因子分别为0.70 kg·m~(-2)·h~(-1)。和860。基于XRD和SEM表征结果,高的渗透汽化性能可归结于在莫来石支撑层与较为疏松的表面晶体层之间形成的致密中间层。     

ZSM-5分子筛酸性质对甲醛合成三聚甲醛催化性能的影响（英文）

ZSM-5分子筛是合成三聚甲醛的有效催化剂。本工作通过XRF、XRD、SEM、NH_3-TPD、Py-FTIR和~(27)Al MAS NMR等手段对一系列不同SiO_2/Al_2O_3物质的量比的ZSM-5分子筛催化剂进行了表征,研究了ZSM-5分子筛中BrΦnsted酸中心和Lewis酸中心对其甲醛合成三聚甲醛催化性能的影响。结果表明,SiO_2/Al_2O_3物质的量比为250的ZSM-5分子筛具有合适的BrΦnsted酸中心用于催化甲醛缩聚为三聚甲醛的反应,同时其Lewis酸中心量极少,可有效抑制Cannizzaro或Tishchenko等副反应,提高三聚甲醛的选择性,因而具有最佳的合成三聚甲醛催化性能。寿命实验评价结果显示,SiO_2/Al_2O_3物质的量比为250的ZSM-5分子筛具有良好的催化稳定性,单程寿命长达114 h,并且可通过550℃焙烧再生恢复其催化活性。     

表面活性剂AEO-3对β沸石合成的促进作用

在常规β沸石的水热合成体系中加入非离子型表面活性剂脂肪醇聚氧乙烯醚(AEO-3),按照n_(Al_2O_3)∶n_(SiO_2)∶n_(Na_2O)∶nTEAOH∶n_(H_2O)∶n_(AEO-3)∶n_(C_2H_5OH)=(0.28～1)∶40∶1.55∶10∶640∶(0.45～7.69)∶11.37的配料比,考察其作为助剂对β沸石合成的影响。实验发现,与常规合成体系相比,AEO-3的加入可促进硅铝酸盐溶胶的生成并增加了其均匀化程度,同时增加了产品收率。所合成样品的X射线衍射、N_2和Ar吸附-脱附、扫描电镜、固体核磁和正癸烷吸附的表征结果表明,表面活性剂AEO-3的加入使β沸石的纳米晶粒更加完整与均匀,提高了结晶度和微孔体积,并使得收率提高。所合成的β沸石的骨架硅铝比提高,酸强度增加。另外,AEO-3的加入提高了β沸石结构中的手性多形体A的比例。     

双矿化剂对合成ZSM-5分子筛酸性和织构特征及其甲醇转化制丙烯催化性能的影响（英文）

采用静态水热法在F~--OH~-体系中,以四丙基氢氧化铵为模板剂、偏铝酸钠为铝源、正硅酸乙酯为硅源,合成了纳米SiO_2-ZSM-5分子筛,考察了F-/Al_2O_3物质的量比对所合成的ZSM-5分子筛织构性质和甲醇转化制丙烯催化性能的影响。结果发现,随着初始溶胶F~-/Al_2O_3物质的量比的增大,产物中SiO_2的含量增大,ZSM-5分子筛的相对结晶度有所降低;同时,分子筛的比表面积和孔容减小、酸强度降低、酸量减少。对于甲醇转化制丙烯,最佳F-/Al_2O_3物质的量比为12;此时,丙烯选择性高于45%,丙烯/乙烯(P/E)比值大于10。反应机理分析表明,过渡态择形选择性是控制烯烃选择性的重要因素。     

n_(Fe~(3+))/n_(Sr~(2+))和n_(OH~-)/n_(NO~-)对锶铁氧体纳米片结构及磁性能的影响

采用改进的水热法成功合成了单分散的纯相锶铁氧体纳米片。借助DLS、XRD、FTIR、SEM、EDS和VSM等分析测试手段对SrFe_(12)O_(19)铁氧体粉体的粒度、结构、形貌和磁性能进行表征。研究结果表明,在240℃保温5 h,物质的量之比n_(Fe~(3+))/n_(Sr~(2+))(R_(F/S))和n_(OH~-)/n_(NO~-)(R_(O/N))分别为5和2时,所得产物为单分散的纯相六角SrFe_(12)O_(19)铁氧体纳米片。随着R_(F/S)和R_(O/N)的变化,合成样品中有少量SrCO_3和Fe_2O_3杂相存在,这主要与反应条件和离子比例有关。磁性能测试结果显示,所得纯相的六角SrF_(12)O_(19)铁氧体纳米片具有优异的磁性能,其饱和磁化强度和矫顽力分别达到60.91 emu·g~(-1)和94.83 kA·m~(-1),使其在医疗、催化和生物等高技术领域具有潜在的应用。     

稻壳基高纯度NaP1沸石的制备及其庚烷异构性能评价

以稻壳为硅源采用煅烧-水热法合成NaP1沸石,考察了不同硅铝比(n_(SiO_2)/n_(Al_2O_3))、水钠比(n_(H_2O)/n_(Na_2O))、晶化温度、晶化时间对沸石结晶度的影响,并以其为载体制备x%Ni/NaP1(x%为Ni与NaP1的质量比)型烷烃异构催化剂。采用X射线衍射、红外光谱、扫描电子显微镜、透射电子显微镜-X射线能谱、N_2气吸附-脱附、X射线光电子能谱、NH_3程序升温脱附、差热分析表征手段对合成材料的晶体结构、微观形貌和金属分散性等进行分析,研究了金属镍掺杂对NaP1酸性和热稳定性能的影响。结果表明以稻壳为硅源制备的NaP1沸石的最佳合成条件为水钠比为35、硅铝比为10、晶化温度为95℃、晶化时间为12 h,此时NaP1晶体的结晶度为99.38%。在以正庚烷异构反应为探针的实验中,4%Ni/NaP1的催化性能最佳,在还原温度400℃、还原时间4 h、重时空速3.52 h~(-1)、反应温度为320℃的条件下,收率最大为46.41%,对正庚烷转化率和选择性分别为65.49%和70.86%。     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

Synthesis of phenolic components of Grains of Paradise

Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.     

Summary of development of the theory of stability of colloids and thin films

In this review, the research of the author in the field of colloidal systems is summarized. The factors influencing colloidal stability are systematized and analyzed. Examples are presented to illustrate the practical utilization of the theory of stability of colloids and thin films.This review was prepared on the basis of the works of the author, which were awarded the State Premium for 1991 in the field of science and technology, chemistry section.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1708–1717, August, 1992.     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.     

氯氧化镁生成热的研究

用氧化镁氯化镁水溶液制备了8水合氯氧化镁[nMg(OH)2·MgCl2·8H2O], 并测定了其在盐酸中的溶解热, 实验结果表明, 氯氧化镁溶解热与n值呈线性关系, 根据溶解热求出5Mg(OH)2·MgCl2·8H2O和3Mg(OH)2·MgCl2·8H2O的生成热分别为-7727.1和5888.1kJ·mol^1^-。     

Thermodynamics of the formation of oxosulfides of rare-earth elements

The enthalpies of solution of several oxosulfides of rare-earth elements and the high-temperature enthalpies of oxosulfides and oxosulfates of lanthanum and yttrium were measured using solution calorimetry and high-temperature microcalorimetry techniques. Standard enthalpies of formation and some thermodynamic properties of oxosulfides and oxosulfates were calculated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2 pp. 294–297, February, 1997.     

探究“铁的锈蚀条件”实验创新设计

设计了铁的锈蚀实验,说明了铁钉的处理方法,增加了温度、酸、碱的影响条件,实现了铁跟蒸馏水及空气中氧气快速反应而生锈,使实验在5 min左右就能够得到准确的结果。