贵金属纳米颗粒复合薄膜光学特性理论研究

采用经典Mie理论模拟计算了Ag、Au和Cu系纳米颗粒复合薄膜的吸收光谱。所有复合薄膜的吸收光谱均在可见光范围内出现表面等离子共振(surface plasmon resonance,SPR)吸收峰。Ag、Au和Cu系复合薄膜的SPR吸收峰峰位和峰强与金属介电常数实部(ε_m1)和虚部(ε_m2)及介质折射率(refractive index,n_s)之间存在强相关性,相比于ε_m1和ε_m2,n_s的增大主导SPR吸收峰向长波方向移动且强度增强。通过改变金属和介质种类可以调节Ag、Au和Cu系复合薄膜的SPR吸收峰峰位和峰强,从而调节其光吸收特性。根据n_s可以推测出金属纳米颗粒复合薄膜在可见光范围内的SPR吸收峰峰位。理论模拟吸收光谱与前人实验结果吻合,SPR吸收峰峰位的理论值与文献实验值接近。     

Au/Al2O3纳米复合薄膜的制备和表征

用溶胶-凝胶法制备了Au/Al₂O₃纳米复合薄膜。利用X-射线衍射、X-射线光电子能谱、原子力显微镜以及紫外-可见光谱对薄膜的微观结构、表面形貌及光学性能进行了表征,研究表明:Au/Al₂O₃纳米复合薄膜是由纳米微晶组成的颗粒膜, 复合薄膜均匀、致密、无裂纹,Au以纳米晶核形式镶嵌于Al₂O₃基体中,纳米Au晶核的粒径为23～26nm;复合薄膜在可见光区有较强的吸收,吸收峰位置与烧结温度有关,吸收强度随烧结温度和金添加量增大而增大。     

双金属核壳结构负载型Au@Ag/TiO2催化剂的制备及表征

利用溶胶法制备了Au核Ag壳(Au@Ag)结构复合纳米粒子,用粉末-溶胶法和水热合成法使其负载于TiO₂纳米粒子上,利用紫外-可见吸收光谱﹑X射线粉末衍射﹑透射电子显微镜对复合结构材料进行了结构表征,并对其光催化消除臭氧的性能进行了研究。结果表明,制备方法、Au/Ag化学计量比及金属负载量等对光催化消除臭氧的活性均有很大影响。采用粉末-溶胶法制备的1%-Au@Ag/TiO₂(n_Au/n_Ag=1∶3)催化剂,由于TiO₂表面沉积的Au@Ag金属颗粒尺寸小且分散度高,而且1%的金属担载量有利于光生电子空穴的有效分离,光催化消除臭氧的活性最高。     

低温吸附制备Au-TiO2复合薄膜及其光电化学性质

在低温条件下将预先合成的Au溶胶吸附到TiO₂薄膜上以制备纳米Au-TiO₂复合薄膜,以超高分辨率场发射扫描电镜(FESEM)、X射线衍射(XRD)及X射线光电子能谱(XPS)表征Au-TiO₂膜,并在UV辐照下测定了Au-TiO₂薄膜电极的光电化学性质。纳米Au呈金属态,平均粒径为(4.3±1.2) nm,负载量高,均匀地沉积于TiO₂薄膜表面。光电化学测试表明,沉积纳米Au后,TiO₂电极的光生电流提高近5倍,光生电压明显向负值增大,说明纳米Au可增强光生载流子的分离效率,促进电荷在电极与溶液界面间的转移。Au-TiO₂电极的电荷传递法拉第阻抗(R_ct)是TiO₂电极的一半,说明负载的纳米Au粒抑制了光生电子-空穴的复合,提高了电极中载流子浓度。     

以镁铝水滑石为前驱体制备复合氧化物催化丙酮气相缩合反应

采用共沉淀-恒温晶化法制备了系列镁铝水滑石(Mg-Al-LDH)样品,对镁铝水滑石在500 ℃焙烧得到镁铝复合氧化物(Mg-Al-LDO),采用IR、XRD、CO₂-TPD、SEM及N₂吸附-脱附等方法对Mg-Al-LDH和Mg-Al-LDO进行了表征。在温度250 ℃、液时空速1 h^-1条件下,采用固定床对镁铝复合氧化物催化剂对丙酮缩合反应的性能进行微反活性评价。研究结果表明,晶化时间与镁铝复合氧化物的弱碱性位和强碱性位的密度相关。丙酮缩聚反应的主要产物为异佛尔酮(IP)和异丙叉丙酮(MO),以及少量的异丙烯基丙酮、双丙酮醇,均三甲苯等。丙酮缩聚制备异佛尔酮的反应需要催化剂表面弱碱性位(S_w)与强碱性位(S_s)的协同作用,S_w与S_s需要匹配。晶化12 h得到的镁铝复合氧化物催化剂(LDO-12)的S_w/S_s=1.3,异佛尔酮(IP)选择性为65.3%,单程有效收率(IP+MO)为14.8%。     

不同nCu2+:nCit3-的Cu(Ⅱ)-Cit3--SiO2溶胶中电沉积制备CuxO-SiO2复合薄膜

以醋酸铜(Cu(Ac)₂)和正硅酸乙酯(TEOS)为前驱体,柠檬酸钠(Na₃Cit)为配合剂,在室温下制备出物质的量之比n_Cu²⁺:n_Cit^3-为1:1和1:2的两种透明稳定的Cu(Ⅱ)-Cit^3--SiO₂复合溶胶。以此为电解液,采用恒电位方法,在ITO阴极上直接制备出了Cu_xO-SiO₂复合薄膜。CV(循环伏安)和XRD(X射线衍射)结果表明,在低过电位和高过电位分别得到Cu₂O-SiO₂和Cu/Cu₂O-SiO₂薄膜。XRD和EDX(X射线散射能谱)结果表明,相同沉积条件下,n_Cu²⁺:n_Cit^3-为1:1溶胶中得到的薄膜中Cu含量较1:2溶胶中的高。薄膜在两种溶胶中的电化学形成机理不同,其原因在于溶胶中Cu(Ⅱ)存在的形式不同。CA(计时安培)和SEM(扫描电镜)结果一致表明,Cu和Cu₂O在两种溶胶中的成核机理与电位有关,随着过电位增大,成核机理从三维连续成核逐渐转向瞬时成核。     

“三明治式”多层Au/Pt复合薄膜的制备及其对甲醇的电氧化

采用界面组装、欠电位沉积和氧化还原置换反应组合方法制备了单层Pt/Au复合薄膜, 并且不需要任何有机偶联剂; 组装单层Pt/Au复合薄膜为三类多层Pt/Au复合薄膜: (Pt/Au)_n、Pt_m/Au和(Pt₃/Au)_k (n、m和k分别为Pt/Au、Pt和Pt₃/Au的层数). 采用电子显微镜研究了Au纳米粒子单层膜和Pt/Au复合多层膜的形貌. 对于所有的多层膜电极而言, 其电化学活性面积随着层数的增加而增加. 通过研究甲醇在每一类Pt/Au复合薄膜上的氧化电流密度, 考察了其对甲醇的电催化和抗毒化性能. 对于同一类复合薄膜而言, 甲醇分别在(Pt/Au)₃、Pt₃/Au和(Pt₃/Au)₂电极上均具有最大的氧化电流密度, 且优于本体Pt电极. 在这三种电极中, (Pt/Au)₃电极无论从电流密度上还是从抗毒化能力上讲, 其性能是最好的, 而且其抗毒化能力也优于商业Pt/C催化剂. 这种良好的催化性能源于Au和Pt之间最大化的协同效应, 这取决于Pt和Au原子比率以及Pt纳米层和Au纳米层之间的排布方式.     

(Au，Ag，Cu)/SiO2二元合金分散复合薄膜非线性光吸收的Mie理论模拟

用修正的Mie理论,模拟计算分析了(Ag,Cu)/SiO2、(Au,Cu)/SiO2、(Ag,Au)/SiO2合金纳米颗粒分散体系的理论吸收光谱。研究发现当二元金属纳米颗粒以合金形式存在时,在一个波段处出现SPR吸收峰,峰位与合金组元的相对含量相关。模拟出的理论吸收光谱与实验结果一致。     

NZFO-PZT磁电复合纳米纤维的制备及其吸波性能

采用静电纺丝法制备(1-x)Ni_0.5Zn_0.5Fe₂O₄-(x)Pb(Zr_0.52Ti_0.48)O₃(简称为(1-x)NZFO-(x)PZT, x=0.1、0.2、0.3、0.4、0.5)磁电复合纳米纤维, 研究了PZT含量对复合纳米纤维结构、电磁特性及微波吸收性能的影响。所有样品均由尖晶石结构NZFO和钙钛矿结构PZT两相所组成。由于NZFO磁损耗与PZT介电损耗的协同效应及界面效应的加强, 适量PZT相的引入可改善复合纳米纤维吸波涂层的电磁阻抗匹配和衰减特性, 提高微波吸收性能。x=0.3和0.4的复合纳米纤维分别在低频和高频范围表现出最强的微波吸收能力。当涂层厚度为2.5~5.0 mm时, x=0.3样品的最小反射损耗在6.1 GHz处达-77.2 dB, 反射损耗小于-10 dB的有效吸收带宽为11.2 GHz(2.8~12.9和16.9~18 GHz);x=0.4样品的最小反射损耗位于18 GHz处为-37.6 dB, 有效吸收带宽达到12.5 GHz(3.3~12.5和14.7~18 GHz)。     

NZFO-PZT磁电复合纳米纤维的制备及其吸波性能

采用静电纺丝法制备(1-x)Ni_0.5Zn_0.5Fe₂O₄-(x)Pb(Zr_0.52Ti_0.48)O₃(简称为(1-x)NZFO-(x)PZT, x=0.1、0.2、0.3、0.4、0.5)磁电复合纳米纤维, 研究了PZT含量对复合纳米纤维结构、电磁特性及微波吸收性能的影响。所有样品均由尖晶石结构NZFO和钙钛矿结构PZT两相所组成。由于NZFO磁损耗与PZT介电损耗的协同效应及界面效应的加强, 适量PZT相的引入可改善复合纳米纤维吸波涂层的电磁阻抗匹配和衰减特性, 提高微波吸收性能。x=0.3和0.4的复合纳米纤维分别在低频和高频范围表现出最强的微波吸收能力。当涂层厚度为2.5~5.0 mm时, x=0.3样品的最小反射损耗在6.1 GHz处达-77.2 dB, 反射损耗小于-10 dB的有效吸收带宽为11.2 GHz(2.8~12.9和16.9~18 GHz);x=0.4样品的最小反射损耗位于18 GHz处为-37.6 dB, 有效吸收带宽达到12.5 GHz(3.3~12.5和14.7~18 GHz)。     

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。