以类水滑石为前驱体的含Cu催化剂催化糠醛加氢反应

 采用共沉淀法制备了不同 Cu 含量的铜镁铝类水滑石 (Cux-MgAl), 再在 500 oC 焙烧制得 Cux-MgAlOy 催化剂. 分别考察了在 220 和 300 oC 还原时, Cu 含量对 Cux-MgAlOy 催化糠醛加氢反应性能的影响. 用 X 射线衍射、H2 程序升温还原、紫外-可见漫反射光谱和 X 射线光电子能谱等技术对催化剂进行了表征. 结果表明, 当 Cu 含量为 11.2% 时, Cu-MgAlOy 催化剂活性和稳定性较高, 糠醛加氢生成糠醇及糠醇进一步加氢脱水的催化活性中心主要是 Cu0, 而催化剂中的 CuO, MgO 和 MgAl2O4 金属氧化物具有催化糠醛与溶剂乙醇反应生成 2-二乙氧甲基呋喃的作用.     

含钯类水滑石衍生复合氧化物Pd/M3AlO(M=Mg,Co, Ni,Cu, Zn)催化剂上氯苯的催化氧化

采用共沉淀法制备了系列含Pd类水滑石材料, 类水滑石基体为M3Al-HT (M=Mg, Co, Ni, Cu, Zn), 经焙烧制备出含Pd类水滑石衍生复合氧化物催化剂. 通过X射线衍射(XRD), 热重-差热分析(TG-DTG), H2程序升温还原(H2-TPR), O2程序升温脱附(O2-TPD)和N2吸脱附等表征技术手段研究了不同二价金属元素对含Pd类水滑石衍生复合氧化物催化剂物理化学性质及其对挥发性有机污染物氯苯催化氧化性能的影响. XRD和TG-DTG结果表明, 不同二价金属元素, 除Cu外, 都能形成类水滑石层状结构, Pd在不同类水滑石前驱物中均能良好分散. 不同的二价金属元素对催化剂性能的影响不同, 其中Pd/Co3AlO催化剂表现出最高的氯苯催化氧化活性, 其起燃温度和全转化温度分别为182和283 ℃. H2-TPR和O2-TPD测试表明, Pd和类水滑石衍生复合氧化物存在着协同作用, Pd的引入促进了复合氧化物的还原, 从而影响氧化物的氧化还原性能. Pd/M3AlO系列催化剂的活性主要受催化剂的氧化还原性能及其表面活性氧物种的影响.     

制备方法对NiCoPrLa类水滑石及其衍生复合氧化物结构及催化性能的影响

用微波法,水热法和微波水热法合成NiCoPrLa类水滑石,并用XRD,TG,TPO,TPR,TPD和FT-IR等对NiCoPrLa类水滑石的晶相结构、热稳定性及相应的衍生复合氧化物的晶相结构、还原性能、吸附性能和抗积碳性能等进行了表征,同时以乙醇水蒸气重整制氢为探针反应考察了制备方法对NiCoPrLa类水滑石的衍生复合氧化物的初活性和选择性的影响.结果表明,制备方法影响类水滑石的结构和热稳定性,水热法制备的类水滑石结晶度较好,微波水热法制备的类水滑石具有较好热稳定性,其中微波水热法所制备的类水滑石衍生复合氧化物具有较好的催化活性和抗积炭性能,在350℃温度下乙醇转化率达到86%.     

含钴铜镍类水滑石焙烧产物催化分解N2O的研究

 合成了含Co，Cu和Ni的M／Mg－Al－HTL类水滑石，并将其焙烧产物用于N2O催化分解反应．实验结果表明，Co／Mg－Al－HTL对N2O分解反应的催化活性明显高于Cu／Mg－Al－HTL和Ni／Mg－Al－HTL的活性．在保持样品中Al含量不变的条件下，催化活性随着Co含量的增加及Mg含量的减少而升高，各催化剂的活性顺序为：Co／Al－HTL＞Co／Mg－Al－HTL＞Cu／Mg－Al－HTL＞Ni／Mg－Al－HTL．在此基础上，进一步考察了Co／Al－HTL中Co／Al原子比调变对催化剂活性的影响．对含Co类水滑石及其焙烧产物进行了XRF，XRD和N2O－TPD表征．结果表明，含Co类水滑石具有典型的水滑石结构，其高温焙烧产物都含尖晶石相．由于尖晶石相中Co－O－Al活性中心的作用，含Co类水滑石对N2O分解反应表现出较高的催化活性．随着Co／Al原子比的增大，含Co类水滑石焙烧产物的尖晶石相特征更加突出，Co－O－Al活性中心数目随之增多，催化剂的活性也相应升高．     

Cu-Mg/Al复合氧化物催化碳颗粒物燃烧性能的研究

恒定二价与三价阳离子比为3(nM2+/nM3+=3),采用共沉淀法制备不同Cu含量的系列水滑石前驱物, 800 ℃焙烧4 h形成复合氧化物(CuO质量百分数分别为0％、5％、10％、15％、20％、30％、40％)用作柴油车排放碳颗粒物燃烧的催化剂,并采用XRD、BET、TG-DSC、FT-IR、TPR等表征手段研究了Cu、Mg含量对材料前驱物物化性能的影响及对其衍生复合氧化物催化碳颗粒物燃烧性能的影响．结果表明,Cu、Mg含量对材料的热稳定性、比表面和催化氧化活性有显著的影响. Mg有助于提高催化剂的热稳定性; Cu含量增加,催化剂比表面下降,但比表面不是影响催化剂活性的主要因素. CuO含量为15％时,催化剂具有最好的催化活性和稳定性,碳颗粒物的起燃温度(T10)和半转化温度(T50)分别为336 ℃和409 ℃.在CuO含量≤30％时可以形成结构完整的水滑石前驱物, CuO含量为40％时出现Cu(OH)2杂相; CuO含量< 20％时,经高温焙烧可得到均匀的复合氧化物, CuO含量≥20％时出现CuO偏析． TPR结果表明焙烧温度和复合氧化物的组成决定了材料的可还原性能．     

CuZnAl类水滑石衍生复合氧化物催化环己醇脱氢反应的研究

采用共沉淀法合成了不同CuZnAl配比的类水滑石,通过不同温度焙烧制备其衍生复合氧化物.采用X-射线衍射(XRD)、差热热重(TG-DTA)、N2吸附-脱附和CO2程序升温脱附法(CO2-TPD)对类水滑石和衍生复合氧化物进行了表征.将所得复合氧化物用于环己醇脱氢制备环己酮的反应中考察其催化活性.实验结果表明:CuZnAl类水滑石衍生复合氧化物对该反应具有很高的催化活性,在反应温度220℃时以CuZnAl[n(Cu)/n(Zn)/n(Al)=1.34/0.66/1.0]类水滑石为前躯体,400℃焙烧所得的衍生复合氧化物表现出最佳的催化活性,环己醇转化率高达94.9%,环己酮的选择性近100%.     

稀土掺杂改性对Cu/ZnAl水滑石衍生催化剂甲醇水蒸气重整制氢性能的影响

采用原位合成法在γ-Al_2O_3表面合成了锌铝水滑石,再通过顺次浸渍法制备了一系列掺杂稀土改性的M(M=Y、La、Ce、Sm、Gd)/Cu/Zn Al催化材料,并将其应用于甲醇水蒸气重整制氢反应。探讨了稀土掺杂改性对Cu/Zn Al催化剂催化性能的影响,并采用XRD、SEM-EDS、BET、H2-TPR、XPS和N2O滴定等手段对催化剂进行了表征。结果表明,催化剂的活性与Cu比表面积和催化剂的还原性质密切相关,Cu比表面积越大,还原温度越低,催化活性越高。稀土Ce、Sm、Gd的引入能改善活性组分Cu的分散度、Cu比表面积以及催化剂的还原性质,进而提高催化剂的催化活性。其中,Ce/Cu/Zn Al催化剂表现出最佳的催化活性,在反应温度为250℃时,甲醇转化率达到100%,CO含量为0.39%,相比Cu/Zn Al催化剂,甲醇转化率提高了近40%。     

铝掺杂对铜铈复合氧化物催化一氧化碳氧化性能的影响

以金属硝酸盐为原料、碳酸钠为沉淀剂,采用共沉淀法制备了一系列Cu0.1Ce0.9-xAlxOy复合氧化物催化剂,并用低温氮气吸附/脱附、X-射线衍射(XRD)和氢-程序升温还原(H2-TPR)等对样品进行了表征,利用微反-色谱评价装置考察了催化剂对CO低温氧化反应的活性,研究了Al含量(x=0～0.3)和催化剂焙烧温度(350、500和650℃)对Cu0.1Ce0.9-xAxOy催化活性的影响。结果表明,随着催化剂中Al含量(x)的增加,Cu0.1Ce0.9-xAlxOy的催化活性先提高,至x=0.1时达到最大,之后又逐渐降低;当催化剂的焙烧温度为500℃时,Cu0.1Ce0.8Al0.1Oy的催化活性最大。Cu0.1Ce0.9-xAlxOy的催化活性与其CuO的还原性之间有较好的对应关系。     

燃料电池用Cu-Ce(La)Ox变换催化剂的制备及性能

采用共沉淀法、沉积沉淀法和超均匀沉淀法制备了30%Cu-Ce-La(10%)Ox型变换催化剂,利用活性测试、XRD和原子吸收等对催化剂的催化性能、晶相结构及组成进行了研究.结果表明,共沉淀法是其中最优的制备方法,氢氧化钠和尿素结合方式沉淀制备的催化剂具有较高的活性和热稳定性.使用NH3·H2O将催化剂中的铜组分滤去的研究结果表明,催化剂中的铜含量存在一最佳值,Cu在形成催化剂活性位时起重要作用,但一旦形成变换反应所需要的活性中心,只要Cu的含量达到一定值后,则Cu的存在与否对催化剂的活性影响不大,甚至过多的Cu对催化活性不利.     

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。     

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.     

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。