Cu/Al2O3催化剂的改性及其对NO选择性还原的催化性能

 以 γ-Al2O3 为载体,采用SO2-4进行改性并添加助剂La,再负载上Cu2+, 制备了改性的Cu/Al2O3催化剂(Cu/La/SO2-4/Al2O3),考察了SO2-4改性和助剂La对催化剂在富氧条件下催化丙烯选择性还原NO 反应的影响,并借助红外光谱、X射线衍射、扫描电镜、热重分析、程序升温还原和X射线光电子能谱等方法研究了改性催化剂的性能与结构的关系. 结果表明,改性催化剂的催化活性较高, NO转化率可高达83.7%. 采用SO2-4改性可促进催化剂表面的酸量增加,并促使产生B酸中心; 助剂La可提高Cu物种的分散程度,并提高催化剂的热稳定性和还原性,从而可有效提高催化剂在富氧条件下对丙烯选择性还原NO反应的催化活性和水热稳定性.     

Cu/HY催化剂在乙炔氢氯化反应中的性能及其失活原因

采用等体积浸渍法制备了以分子筛为载体的铜基无汞催化剂(Cu/HY),在固定床反应器中,考察了Cu/HY催化剂用于乙炔氢氯化反应制取氯乙烯的催化性能,并采用扫描电子显微镜(SEM)、能量散射光谱(EDS)、电感耦合等离子光谱(ICP-AES)、氮气吸脱附(BET)、热重分析(TG)、透射电子显微镜(TEM)、X射线粉末衍射(XRD)和X射线光电子能谱(XPS)表征手段对反应前后的催化剂进行了表征和分析。 结果表明,反应温度为160 ℃,常压,空速为120 h^-1,V(HCl)/V(C₂H₂)=1.25,Cu的负载质量分数为15%时,Cu/HY催化剂的乙炔氢氯化性能最佳,乙炔转化率可达84%,氯乙烯选择性始终大于95%,且具有较好的稳定性;通过表征分析,认为催化剂表面形成积碳,铜活性物种的还原、团聚和流失是导致Cu/HY催化剂活性下降的主要原因。     

双金属NiCu/MgO催化剂上葡萄糖氢解制备高附加值C2-C4化学品（英文）

采用共沉淀法制备了不同Ni/Cu比的NiCu/MgO双金属催化剂,并通过N_2物理吸附、X射线衍射(XRD)、X射线光电子能谱(XPS)和程序升温还原等方法对NiCu/MgO催化剂结构进行表征.表征结果表明,Cu和Ni之间存在协同相互作用,NiMgO_2的存在抑制了镍物种的还原和Cu-Ni合金的形成,催化剂的Ni/Cu比和焙烧温度对其表面金属组成有非常重要的影响.以葡萄糖氢解反应为探针反应,考察了Ni/Cu比、焙烧温度、H_2压力、反应温度、反应时间等因素对NiCu/MgO催化性能的影响.研究表明相对于单金属催化剂,双金属催化剂对葡萄糖氢解生成C2-C4和1,2-PD具有较高的催化活性,这与铜镍之间的协同作用有关.     

Fe柱撑海泡石负载Cu催化剂：结构特点及其C3H6选择性催化还原NO催化性质

通过羟基铁离子柱撑将海泡石(Sep)改性成Fe柱撑海泡石(Fe-PILSEP),使用浸渍法(IM)将Cu负载在Fe-PILSEP上,制得不同铜含量的xCu/Fe-PILSEP催化剂。通过X射线衍射(XRD)、N2-吸附/脱附、H2-程序升温还原(TPR)和X射线光电子能谱(XPS)等对样品进行表征,并测定其对丙烯选择性催化还原NO的催化活性。N2-吸附/脱附和TGA结果表明,Fe-PILSEP的比表面积和孔体积较海泡石原矿Sep极大地增加,热稳定性也明显优于Sep。XRD和XPS结果表明,在xCu/Fe-PILSEP催化剂上同时存在Fe3+/Fe2+和Cu2+/Cu+不同氧化态的氧化物,而且Fe与海泡石之间存在相互作用,Fe和Cu之间存在电子迁移。H2-TPR结果表明,xCu/Fe-PILSEP催化剂上存在不同聚集状态的氧化铜物种。xCu/Fe-PILSEP催化剂的丙烯选择性催化还原NO的催化活性明显优于Fe-PILSEP催化剂,这可能与Fe和Cu的氧化还原性有关。xCu/Fe-PILSEP的催化活性与Cu负载量相关,其中10Cu/Fe-PILSEP催化剂显示出最高的活性,这与其高的比表面积、孔体积和氧化还原性能,及其具有更多有利于HC-SCR反应的孤立Cu2+((Cu2+)i)物种有关。     

不同载体负载的Cu2(OH)3CI催化剂对甲醇氧化羰基化的催化性能

采用浆液浸渍法制备了小同载体负载的Cu2(OH)3Cl催化剂,考察了催化剂对甲醇氧化羰基化合成碳酸二甲酯(DMC)反应的催化性能.结果表明,各载体负载的Cu2(OH)3Cl催化剂活性均高于传统的负载CuCl2催化剂;以比表面积较大的活性炭(AC)为载体的催化剂活性最高.以Cu2(OH)3Cl/AC(w(Cu)=18.71%)为催化剂时,甲醇转化率、DMC选择性和DMC时宅收率可分别达到6.93%,67.3%和139.1mg/(g·h);其催化性能比较稳定,反应60h后其催化活性略有下降.通过CO程序升温脱附、X射线衍射、X射线光电子能谱和扫描电镜等技术对催化剂进行了表征.结果表明,在反应过程中催化剂的活性物种Cu2(OH)3Cl的晶粒逐渐团聚、长大,并且转化为CuCl2和CuO;同时,新鲜催化剂中唯一的CuⅡ物种部分转化为CuⅠ物种.     

Cu/SiO_2结构及其催化苯酚羟基化反应性能的研究

以不同结构的SiO_2为载体,采用传统浸渍法,合成3种负载型的Cu/SiO_2.使用X射线衍射(XRD)、 N_2的等温吸-脱附、紫外漫反射光谱(DR UV-vis)、 X射线电子能谱(XPS)、等离子原子发射光谱(ICP)和H_2的程序升温还原(H_2-TPR)方法对样品进行表征.考察了以H_2O_2为氧化剂,样品对苯酚直接羟基化合成苯二酚的催化性能.结果表明:具有介孔和MFI结构的二氧化硅(MS-1),稳定性强,有利于引入Cu物种在其孔内扩散及分布,形成更多的高分散CuO.一定反应条件下, Cu/MS-1催化活性最高,苯二酚的收率和选择性分别高达38.91%和81.5%. Cu/MS-1催化剂重复使用10次后,苯二酚的收率为37.64%,而Cu含量仅从2.5%变为2.1%,具有较强稳定性;高分散CuO是目标反应的主要活性物种.     

Cu掺杂对介孔VOx-TiO2催化苯羟基化制苯酚的影响

将Cu作为第二金属,制备了不同Cu掺杂量的和不同温度下焙烧的双金属改性的Cu/VOx-TiO2复合催化剂,并用于液相苯直接羟基化制苯酚反应中.固定钒的含量为4.3%,合成了一系列不同Cu掺杂量(w=0.29%~2.5%)的催化剂,并在不同的温度下(350~650°C)进行了焙烧.利用X射线衍射、N2吸附-脱附、扫描电镜、透射电镜、H2程序升温还原以及X射线光电子能谱对催化剂进行了表征.结果表明,加入Cu后催化剂仍保持有序的介孔结构,并且有效地促进了VOx物种在载体TiO2上的分散和VOx物种的还原,同时提高了催化剂的热稳定性,其中Cu以+2价的形态存在于催化剂中.另外,考察了催化剂用量,反应温度等对苯羟基化反应性能的影响.     

CuO/SBA-15催化剂上巴豆醛选择性加氢

通过γ-氨丙基三甲氧基硅烷(APTS)偶联与Cu2 离子络合两步法将CuO负载到介孔分子筛SBA-15上,制得CuO/SBA-15催化剂,考察了催化剂的巴豆醛选择性加氢反应性能.通过X射线粉末衍射、氮气吸脱附和程序升温还原(TPR)技术对催化剂进行了表征.结果表明,SBA-15分子筛负载CuO后保持原有的介孔结构,但是孔容和比面表积随着CuO负载量的增大而下降.TPR结果表明CuO/SBA-15系列催化剂有三种CuO物种:高分散CuO、晶相CuO和进入SBA-15分子筛骨架的Cu2 .高分散CuO物种对巴豆醛加氢反应的催化活性最高,晶相CuO物种次之,而进入SBA-15分子筛骨架的Cu2 物种几乎没有活性.     

CuO-Bi2O3/SiO2-MgO催化剂的制备及炔化性能

采用浸渍法、沉积-沉淀法、共沉淀法制备了CuO-Bi2O3/SiO2-MgO催化剂,利用低温N2物理吸-脱附、透射电镜(TEM)、X射线衍射(XRD)、H2程序升温还原(H2-TPR)、傅里叶红外(FT-IR)等技术对其进行了表征,并考察了催化剂在甲醛乙炔化合成1,4-丁炔二醇反应中的催化性能.结果表明,制备方法对催化剂中活性组分分散度及还原性能有较大影响,进而在甲醛乙炔化合成1,4-丁炔二醇反应中表现出不同的催化活性.采用共沉淀法制备的催化剂中活性物种CuO具有高的分散度与较好的还原能力,经活化后可生成数量较多的炔铜配合物活性中心,表现出最佳的炔化反应活性与丁炔二醇选择性.     

以拟薄水铝石为铝源制备浆态床二甲醚合成催化剂

利用完全液相法, 以拟薄水铝石(AlOOH)为铝源制备了CuZnAl浆状催化剂, 并通过添加不同的干燥控制化学添加剂(DCCA)对催化剂前驱体进行了修饰, 采用X射线粉末衍射、氮气吸附、X射线光电子能谱和程序升温还原对其进行了表征, 考察了CuZnAl浆状催化剂在一步法合成二甲醚反应中的催化性能. 实验结果表明, 以AlOOH为铝源, 所得样品的Cu和Al间相互作用较强, 生成了CuAl2O4相, 从而减少了催化剂中可还原Cu2O的数量, 降低催化活性. 添加不同DCCA对催化剂性能有显著的影响, 其中加入丙三醇增加了催化剂的比表面积和平均孔径, 改善了催化剂组分的分散性, 抑制了CuAl2O4的形成, 提高了催化剂中的可还原Cu2O量, 从而显著提高了催化剂的二甲醚时空收率和选择性.     

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.     

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。     

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^-。     

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。