两种甲醇水蒸气重整制氢催化剂的研究

对采用共沉淀法制备的CuZnAlO类铜系催化剂和采用水滑石类层柱材料（LDHs）前驱体制备的催化剂在甲醇水蒸气重整制氢反应中的性能进行了研究。对共沉淀法制备的CuZnAlO类铜系催化剂考察了ZrO2助剂的加入对催化剂反应性能的影响，发现Zr的质量分数为10％的催化剂显著提高CuZnAlO催化剂的反应性能。该催化剂的最佳反应条件：0.1 MPa、250 ℃、H2O/MeOH摩尔比1.0～1.3、3.56 h－1。在此反应条件下进行了COPZr2催化剂150 h稳定性实验。结果表明，该催化剂具有很好的反应稳定性。甲醇转化率和氢产率分别约为88％和83％，产物湿基组成中H2和CO的质量分数分别为>63％和0.20％～0.31％。对LDHs前驱体制备的催化剂，进行了70 h反应稳定性实验，结果表明，催化剂虽具有较高的起始活性，但随反应进行，活性有所下降，30?h后基本保持稳定，甲醇转化率和产氢率分别为73％和66％，产物湿基组成中H2和CO的质量分数分别为>55％和0.07%～0.08%。该类催化剂的反应稳定性虽较差，但却可以显著降低产物湿基组成中CO的摩尔分数。对LDHs前驱体制备的催化剂进行XRD和SEM表征结果表明，ZrO2的加入使催化剂中CuO晶粒分散更为均匀，颗粒更细。     

海刺猬状微纳结构钴镍化合物的合成与表征(英文)

采用均相沉淀法,以Co(NO_3)_2·6H_2O和Ni(NO_3)_2·6H_2O为原料,尿素作为沉淀剂,成功制备出了新型海刺猬状微/纳复合结构。通过调节反应温度,反应物浓度和物质的量的比,所获得的前驱体呈放射状纳米线构成的海刺猬结构。随后分别在氧气氛和氢气氛下对制备出的前驱体进行热处理,利用FE-SEM、TEM、XRD以及VSM等测试手段对制备出的微/纳复合结构前驱体及热处理产物进行了形貌表征、物相分析以及磁学性能表征。在氧气氛条件下处理得到的产物具有良好的亚铁磁性,并且很好地保持了前驱体的结构与形貌。结合热处理产物的分析,对该海刺猬微纳结构前驱体提出了一种可能的形成过程和机理。另外,在氢气还原条件下处理得到的产物为多孔微纳米球状结构,呈现出更为优异的亚铁磁性。     

锂离子交换剂制备及交换反应动力学

通过XRD分析、Li＋抽出率βLi及Mn2＋溶出率γMn的计算，考察了不同焙烧温度及抽锂剂对前驱体锂锰氧化物LiMn2O4结构及稳定性的影响.结果表明, 750 ℃下焙烧2 h，并使用过硫酸铵(NH4)2S2O8作抽锂剂，制备的Li＋交换剂MnO2(Li)对Li＋的交换容量αLi较大.另外，通过Li＋在固液两相间分配系数的测定及交换反应动力学实验，对离子交换反应机理进行了研究，并建立了有限浴条件下MnO2(Li)离子交换反应动力学模型.结果表明,该离子交换过程近似符合颗粒扩散控制；交换反应主要发生在交换剂颗粒外层；提出的动力学模型与实验结果符合较好.     

O2结构Liy[Mn1—xMx]O2（M＝Cr，Mg）的合成及结构研究

由高温焙烧法制备层状前驱体Na_(2/3)[Mn_(1-x)M_x]O_2（M＝Cr, Mg），再 经离子交换反应得到层状O2结构产物Li_y-[Mn_(1-x)M_x]。XRD表明Li_y[Mn_(1-x) M_x]O_2属六方晶系，P3ml空间群。Cr的添加量对前驱体的晶体结构有很大影响： 随着x值的增大，前驱体逐渐由层状P2结构Na_(2/3)[Mn_(1-x)Cr_x]O_2向正交结构 Na_4Mn_90_(18)转变。由SEM可以看到样品Li_y[Mn_(1-x)Cr_x]-O_2(x≤0.05)具有 六方层状结构。XPS分析结果表明样品Li_y[Mn_(0.95)Cr_(0.05)]O_2表面上的Mn和 Cr分别以Mn~(4+)存在，并且表面中Cr相对含量高于体相，而样品Li_y[Mn_(0.90) Mg_(0.10)]O_2的表面Mn和Mg分别以Mn~(4+)和Mg~(2+)存在，Mg/Mn比在表面与体相 基要一致。     

离子交换法制备层状LixNi0.3Mn0.7O2正极材料及其离子交换规律的研究

通过共沉淀法高温固相反应在空气气氛中合成出具有P2型结构特征的碱青铜前驱体Na_0.66Ni_0.3Mn_0.7O₂，研究了在4种不同离子交换条件下进行离子交换反应得到目标正极材料Li_xNi_0.3Mn_0.7O₂的离子交换规律，并用XRD、SEM、粒度分析和电性能测试考察了目标正极材料及其前驱体的结构、形貌和电化学性能。结果表明，以熔融LiNO₃为介质于300 ℃离子交换4h反应进行得最为完全，离子交换率达98 %，且目标正极材料具有较完善的O2型层状结构，在2.6～2.9 V存在唯一的充放电平台，循环过程中未发现向尖晶石相转变；而离子交换时间过长，目标正极材料将出现尖晶石相而影响其放电容量和循环稳定性。     

氟尿嘧啶与磁性层状复合氢氧化物的离子交换反应动力学

以共沉淀法合成的磁性层状复合氢氧化物(Magnetic layered double hydroxide, MLDH)为前驱体, 通过对原位反应系统液相数据的拟合与固相样品的表征, 研究了0~50 ℃条件下MLDH与氟尿嘧啶(5-FU)的离子交换动力学特征. 结果表明, MLDH及离子交换产物MLDH-FU为以六方晶系为主并混杂微量氧化铁的复合磁性晶相; MLDH-FU离子交换速率随温度的升高而显著加快, FU, OH^-和Cl^- 3种客体的浓度变化分别服从二级、 零级及一级反应速率模型, 反应活化能依次为12.69, 27.88和3.580 kJ/mol. 固相表征参数的变化与液相动力学过程、 主-客体结构调整及MLDH-FU粒子陈化过程相符; 离子交换限定在LDH层间, 不涉及层板内部秩序, 不改变前驱体的结构与形貌特征, 具有侧向非断层反应习性, 是交换剂在MLDH外周经吸附亲和、 侧向进攻、 层间置换及柱撑模型转换再到新的插层客体主导调整及晶粒发育陈化的有序过程.     

孔壁含有沸石次级结构单元的MCM-48的合成及催化研究

以双表面活性剂（双极性头表面活性剂和三乙醇胺）为模板，以含有沸石次级结构单元的溶胶为前驱体，在碱性条件下合成了新型介孔分子筛MCM 48。研究了沸石前驱体和三乙醇胺对产物MCM 48形成的影响，XRD和TEM表征结果表明，样品具有较高的结晶度和规则的孔径；FTIR和N2吸附表征结果表明，产物MCM 48的孔壁中含有沸石的次级结构单元，从而使得样品具有更大的比表面积。产物的重芳烃轻质化反应催化活性表明，实验样品对重芳烃的转化率比常规的MCM 48高，转化率约高出11%，进一步证明了实验样品的孔壁中含有沸石的结构单元。     

水热法制备掺杂铁离子的TiO2纳米粒子及其兴催化反应研究

以TiCl4为前驱体，采用水热法制备了掺杂铁离子的TiO2纳米粒子，利用XRD对不同条件下制备的产物进行了表征，探讨了反应温度、胶体溶液pH值和反应时间对水热反应的影响。考察了所制备的Fe^2 -TiO2纳米粒子光催化降解罗丹明B的催化性能，实验发现，制备的掺杂0．1％Fe^3 -TiO2纳米粒子与纯TiO2相比，具有更好的催化活性。     

利用Kirkendall效应制备Ce1-xTixO2中空纳米球

利用Kirkendall效应, 在溶剂热条件下成功制备了复合氧化物Ce_1-xTi_xO₂的纳米空心球, 并通过XRD, TEM和XPS等测试手段进行了表征. 结果表明, Ce_1-xTi_xO₂纳米空心球的粒径为65 nm, 小于初始状态的CeO₂纳米球, 并且Ce_1-xTi_xO₂纳米空心球的结构与前驱体CeO₂晶体结构相同, 均为面心立方结构. Ti/Ce摩尔比和温度是影响产物形貌和结构的重要因素, 通过实验得出最佳反应条件为n(Ti)∶n(Ce)=8∶10, 于190 ℃反应8 h.     

室温下制备Cu7S4和Ag2S的球形空心纳米粒子

以Cu₂O和Ag₂O纳米粒子为前驱体,利用Kirkendall效应,在室温条件下制备出Cu₇S₄和Ag₂S的球形空心纳米粒子。用X-射线衍射(XRD)、透射电镜(TEM)、扫描电镜(SEM)等测试手段对产物进行了表征。结果表明,粒子的空心化程度取决于反应物的物质的量之比;空心粒子的形貌与前驱体粒子的形貌很相似。研究了这种反应的机理,并对这两种氧化物发生这类反应的难易程度作了理论探讨。     

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。