介孔二氧化钛的合成及其对甲基橙降解的光催化活性

以十六烷基三甲基溴化铵为模板剂,通过水解钛酸正丁酯合成了介孔二氧化钛分子筛,探讨了合成条件的影响。采用X射线粉末衍射(XRD)、红外光谱(FT-IR)、透射电子显微镜(TEM)和N2吸附-脱附等技术对介孔二氧化钛的晶相、结构、形貌、比表面积和孔径分布进行了表征。实验结果表明:得到的介孔二氧化钛分子筛的孔径为4-4.3nm,用抽提的方法去除模板剂得到的介孔二氧化钛的比表面积比焙烧的要高。以甲基橙为模型污染物,检验了所合成介孔二氧化钛的光催化性质。     

TiO2介孔分子筛的光催化制氢活性Ⅱ:热稳定性的影响

以三乙醇胺为模板剂,合成了具有蚯蚓状孔道结构的高比表面积二氧化钛介孔分子筛.通过用XRD,BET法等手段对其进行表征,考察了用萃取法脱除模板剂后二氧化钛介孔分子筛的热稳定性,并发现其与光催化制氢反应相关联,同时探讨了催化剂比表面积、晶型对其催化活性的影响.     

新型孔结构渣油催化裂化催化剂

高温短接触FCC工艺和原料的重质化要求FCC催化剂具有大孔，以增加大分子烃在催化剂中的扩散速度，提高催化剂的反应性能。在不改变催化剂组成的前提下，采用聚苯乙烯微球为模板剂在催化剂基质中引入适量的、尺寸可控的大孔；通过SEM、N2吸附等对催化剂的形貌和孔结构进行了表征；以大庆常压渣油为原料，测定了催化剂的反应性能。实验表明，大孔催化剂中孔体积和比表面积随模板剂用量的增加而增加；在模板剂用量相同时，模板剂粒径越小孔体积和比表面积增加越多。模板剂的引入不仅增加了催化剂中的大孔孔体积，使得催化剂中微孔部分的体积和比表面积也有了一定增加。模板颗粒法合成的催化剂，扩散阻力小，重油转化率高，轻油收率高。     

介子LSBA-15中有机模板剂的紫外／臭氧法脱除

紫外／臭氧法用于脱除有序介孔材料SBA-15中有机模板剂．该方法是-种非加热光化学降解法，简单、易操作，可在温和条件下彻底除去SBA-15中三嵌段共聚物有机模板剂P123．通过XRD，TEM，FT—IR和BET等对SBA-15经不同方法脱除模板剂前后的详细表征，表明紫外／臭氧法在彻底脱除SBA-15中有机模板剂后，保留了很好的骨架有序性，比表面积更大，孔道更加开放，克服了高温焙烧脱除模板剂造成的孔道收缩．     

有序中孔炭的制备及电性能研究

采用微湿含浸法制备了一系列具有不同比表面积和孔径分布的超级电容器有序中孔炭材料,同时采用Al-SBA-15为模板剂制得具有六方排列的空心炭管CMK-5.所制得的有序中孔炭的BET比表面积随糠醇加入量的增加而减小.电化学性能测试结果表明,在1mA·cm-2的充放电电流密度下各中孔炭材料比电容的大小顺序与其BET比表面积的大小顺序相一致.在所有样品中AlSC-0.8由于具有最大的比表面积,因此其比电容最大,达87.8F·g-1.倍率性能测试结果表明,具有CMK-3结构的SC-2.0的倍率性能最好,在50mA·cm-2的放电电流密度下其放电比电容接近AlSC-0.8有序中孔炭的水平.     

介孔SBA-15中有机模板剂的紫外/臭氧法脱除

紫外/臭氧法用于脱除有序介孔材料SBA-15中有机模板剂. 该方法是一种非加热光化学降解法, 简单、易操作, 可在温和条件下彻底除去SBA-15中三嵌段共聚物有机模板剂P123. 通过XRD, TEM, FT-IR和BET等对SBA-15经不同方法脱除模板剂前后的详细表征, 表明紫外/臭氧法在彻底脱除SBA-15中有机模板剂后, 保留了很好的骨架有序性, 比表面积更大, 孔道更加开放, 克服了高温焙烧脱除模板剂造成的孔道收缩.     

纯二氧化钛介孔分子筛的合成与表征

分别用不同链长的烷基磷酸酯和脂肪胺两类不同表面活性剂为模板剂合成了纯二氧化钛介孔分子筛（Ti-TMS1，Ti-TMS2），并用溶剂法代替高温焙烧法成功地脱除了模板剂。用 XRD、TEM等测试手段对这类材料的结构进行了表征，研究了反应条件对所制备样品的结构的影响。结果表明：得到的纯二氧化钛介孔分子筛为较规则的六角堆积排列，孔径为2.7～4.4 nm, 且其纳米孔径大小可以通过改变烷基磷酸酯模板剂的烷基链长而调节。此外还发现，采用的烷基磷酸酯模板剂的烷基链越长，制得的二氧化钛介孔分子筛结构及晶型的完整性越好。进一步的研究表明，模板剂脱除之后，Ti-TMS2结构的晶体完整性和稳定性明显不如Ti-TMS1的好，且Ti-TMS1的介孔结构优于Ti-TMS2的介孔结构。     

沉淀条件对稀土氧化物的比表面积和形貌的影响（Ⅱ）

以稀土元素Nd,Eu和Y为对象，利用比表面积分析仪和扫描电镜考察了各种沉淀条件对稀土氧化物的比表面和形貌的影响。结果表明：降低沉淀温度和提高加料速度有利于获得较大比表面积的产品，但不利于产颗粒晶型的完整化。稀化与草酸的比例以及陈化时间对样品的比表面积影响不大，但增加陈化时间，有利于改善氧化物颗粒的晶型以及尺寸分布。因此，在工业生产中，为了提高产品质量，陈需控制的烧条件外，还应注意控制沉淀温度、加料速度和陈化时间。     

酚醛树脂基球形微-介双阶多孔炭的软模板法制备

将苯酚和甲醛在碱性条件下聚合,然后在酸性条件下与软模板剂F127自组装形成中间相,经高温煅烧合成球形微-介双阶多孔炭。 通过扫描电子显微镜、透射电子显微镜、氮气吸附-脱附和热重分析技术对样品进行了形貌观察和性能测试。 结果表明,pH值、软模板剂用量和活化温度对样品形貌有调控作用。 当软模板剂F127的质量分数为20%、pH值为0.5和活化温度为700 ℃时,可制备出直径为100～200 nm的球形炭,球形粒子分散均匀,排列规整,呈明显蠕虫状排列的孔隙结构,比表面积为503 m2/g,孔容积0.416 cm3/g,介孔孔径集中分布在2.9 nm,微孔主要分布在1.3 nm。 随着活化温度升高,炭球的比表面积和孔容积增大,平均孔径减小。 F127的热解形成介孔结构,碳前驱体高温下的径向收缩形成微孔结构。     

模板剂及Ni掺杂对中孔TiO2材料性能的影响

1992年美国Mobil公司首次报道了以离子型表面活性剂为模板剂通过水热法合成了中孔二氧化硅及硅铝材料，由于此类材料具有较大的孔径和比表面积以及优良的吸附性能，在较大的分子或基团的反应中具有较大的优势，引起了催化、吸附分离、无机合成及材料科学等许多领域研究者的广泛关注，许多不含硅的具有半导体性能的中孔氧化物材料在光催化、气体传感、局部氧化、完全燃烧、NOx降解、加氢脱硫等方面显示出优良的性能，二氧化钛是一类应用很广的氧化物。     

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。