化学气相沉积法制备Ti/HMS催化剂及甲基接枝改性

用化学气相沉积法制备了Ti/HMS介孔分子筛催化剂, 并对其进行甲基接枝改性. 用XRD、N2-吸附、ICP-AES、FTIR, UV-vis和29Si CP/MAS NMR等手段对样品进行了表征, 考察了催化剂的丙烯环氧化性能. 结果表明: 气相沉积法载钛和接枝改性减小了HMS分子筛表面的孔径和比表面, 但是分子筛的介孔特征仍然保持; 随着沉积时间的增加(0.5～2 h), 催化剂的钛含量逐渐增加, 催化活性也随之增加, 但当沉积时间超过2 h后, 钛含量和催化活性均保持不变; 接枝改性后催化剂的环氧化活性和选择性均显著提高; 气相沉积法合成Ti/HMS比水热法合成Ti-HMS具有更高的环氧化催化活性.     

铈掺杂对Co_3O_4/微孔-介孔分子筛催化剂催化性能的影响

采用水热法制备了微孔-介孔分子筛,并以Ce掺杂改性后制备了Co3O4/Ce-微孔-介孔分子筛催化剂,考察了Ce掺杂微孔-介孔分子筛催化剂对苯催化完全氧化性能的影响,并采用BET,XRD,TPR等技术对催化剂进行了表征。研究结果表明:Ce的加入有利于提高MSZ-B催化剂的催化活性。XRD分析显示Ce的加入不会阻塞Co3O4在微孔-介孔分子筛孔道内的分布;TPR分析表明:Ce的加入提高了MSZ-B催化剂的可还原性能,催化剂的可还原性能是影响催化活性的主要因素;另外,介孔的存在不利于Ce改性Co3O4/ZSM-5微孔分子筛催化剂活性的提高。     

ZSM-5酸改性对甲醇芳构化性能的影响

利用硝酸、草酸和酒石酸溶液对ZSM-5分子筛进行改性,并采用XRD、SEM、NH₃-TPD、XRF、²⁷Al MAS NMR、吡啶吸附红外光谱和N₂吸附-脱附对ZSM-5分子筛结构、酸量、比表面积及孔体积等物化性质进行表征分析。在反应温度为422℃,甲醇质量空速为4.74 h^-1的条件下,考察了ZSM-5分子筛的催化活性。结果表明,采用不同酸改性ZSM-5分子筛,影响了分子筛的比表面积、酸性及孔体积,从而改变了催化剂的催化性能。在甲醇芳构化（MTA）反应中,酸改性后的分子筛表现出良好的催化活性,且草酸改性后的催化剂表现出较高的催化活性及选择性,反应8 h时,芳烃及BTX收率分别达到57.40%和39.40%。     

孔径对锆同构替代的Co/SBA-15催化剂费-托合成催化性能的影响

采用同构替代方法将锆掺杂进入SBA-15中孔分子筛的骨架中,通过控制合成条件合成出了锆硅摩尔比为1/20的具有四种不同孔径(5.7,7.8,11.6,17.6nm)的Zr-SBA-15中孔有序锆同构替代改性分子筛,并在该改性分子筛上负载质量分数为10%的钴制备出用于费-托合成的钴基催化剂.采用氮气吸附-脱附、XRD、H2-TPR、H2-TPD及氧滴定实验、TEM、29Si固体核磁共振光谱(29SiNMR)、XPS等手段对催化剂进行了表征,系统地研究了同构替代锆掺杂SBA-15分子筛孔径大小对钴基催化剂费-托合成催化活性和产物选择性的影响.同时也采用了原位X射线衍射技术考察了载体孔径对催化剂的还原性能的影响,并结合催化剂的X光电子能谱表征结果进一步讨论了孔径对钴-载体相互作用的影响,为孔径对催化剂的活性以及产物选择性的影响作出了合理的解释.研究结果表明:随着孔径增加,SBA-15中孔分子筛的二维六方有序结构逐渐破坏,催化剂的比表面积下降,钴-载体相互作用降低,钴的晶粒直径增大,催化剂的还原性增加,C5+选择性增加,CO转化率先升高后降低,孔径为7.8nm的催化剂具有更好的费-托合成催化活性,这是催化剂比表面积和...     

Ga、Zn改性方法对HZSM-5催化剂丙烯芳构化性能的影响

以浸渍法和水热合成法对ZSM-5分子筛进行Ga、Zn改性,制得不同酸性的分子筛催化剂。采用XRD、SEM、NH3-TPD和XPS等表征手段,研究考察了Ga、Zn和不同引入方法对催化剂的孔结构、骨架结构特性和表面酸性的影响,并以丙烯芳构化为模型反应,考察了Ga、Zn改性对ZSM-5催化剂烯烃芳构化催化性能的影响。研究结果表明,Ga、Zn改性对催化剂形貌影响较小,但能明显改变催化剂的表面酸性和烯烃芳构化性能。Zn改性能降低催化剂的酸性,而Ga改性与其引入的方式有关,浸渍法引入催化剂的中强酸位略有下降,而水热合成法引入则显著增加了催化剂的总酸量。Ga、Zn改性均提高了芳构化反应的活性和芳烃选择性,并抑制催化剂表面积炭。     

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.     

不同沸石分子筛对乙基叔丁基醚合成反应的催化性能

 研究了液相、加压条件下，不同沸石分子筛对低温合成乙基叔丁基醚（ETBE）的催化性能．发现Hβ沸石的催化活性与A－35树脂催化剂的相当，远远高于其他沸石分子筛催化剂．醇／烯比对Hβ分子筛催化剂及A－35催化剂上ETBE的合成影响比较大．但是Hβ沸石分子筛上ETB E的选择性基本不受醇／烯比的影响，而醇／烯比对树脂催化剂上ETBE的选择性影响相对较大．加入粘合剂后，Hβ沸石分子筛催化剂的活性有所下降，但是加入致孔剂后，其活性有所提高．加入5％聚乙二醇4000后，在温度高于65℃时，Hβ沸石的催化活性已经与A－35的相当，在某些温度下，甚至高于A－35树脂催化剂的活性．     

苯酚和草酸二甲酯在不同分子筛催化下的酯交换反应

研究了以TS－1、H－ZSM－5、Hβ和H－丝光沸石等不同分子筛为催化剂，苯酚和草酸二甲酯酯交换合成草酸二苯酯反应。通过对催化剂进行吸附吡啶的红外光谱和NH3－TPD表征，考察了不同分子筛催化剂的酸性和酸强度对草酸二苯酯合成反应的影响，确定了催化剂上的弱酸中心是催化苯酚和草酸二甲酯酯交换合成草酸二苯酯反应的活性位，且催化剂的酸性中心越多，酸量越大，催化活性越好。催化剂上的强酸中心促进了副产物苯甲醚的生成。     

硅基分子筛及其在精细化学品合成中的应用*

本文综述了沸石分子筛及中孔硅基材料在合成方面的最新进展,总结了这类分子筛材料在精细化学品合成中的应用及取得的成果,详细介绍了中孔分子筛的表面改性尤其是有机－无机杂化分子筛的合成、性质、特点及其作为催化剂在有机合成反应中的应用。     

SAPO分子筛的酸性及其孔道分布对丁烷异构脱氢反应的影响

 合成了四种磷铝及硅磷铝系列分子筛,并用XRD表征了分子筛的晶体结构,用X荧光光谱测定了其元素组成,用NH3－TPD和物理吸附考察了其酸性和孔道分布．考察了以合成的分子筛为基质制备的催化剂上丁烷异构脱氢反应的性能．结果表明,以弱酸性的SAPO－5分子筛和孔口狭窄的SAPO－34分子筛为载体的催化剂,它们的催化性能较差;以十元环的SAPO－11分子筛为载体的催化剂显示出较高的活性和选择性．同时,考察了不同分子筛催化剂上Pd金属粒子的分散状态,分析了分子筛的酸性和孔道结构对反应性能的影响．     

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.     

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.

     

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。     

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.     

恶臭嗅辨实验室建设探讨

针对恶臭测试的环境影响问题,提出了解决的实例方案,并对方案的要点及优缺点进行讨论,此方案在实际操作中具有较好的效果。     

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.     

解决能源问题的新途径——光解水制氢的研究

面对日益枯竭的能源危机,氢能是一种洁净、最有前景的替代能源。目前在各种制氢的方法中光催化分解水制氢的研究最多,光解水过程中催化剂最关键,本文对利用太阳能光解水的途径、提高光催化反应效率以及光催化剂的开发研究进行了综述。     

黄酮化合物的合成研究进展

黄酮化合物是一类具有多种生物活性的天然产物,其经典的合成方法主要为查耳酮路线和β-丙二酮路线.近年来出现了许多新技术、新方法.本文介绍了2'-羟基查尔酮的氧化关环法、黄烷酮氧化法、改进的Baker-Venkataraman法及其他合成黄酮化合物的方法.