用于乙烯环氧化反应的CuCs掺杂银基催化剂设计

最近的理论研究筛选出CuCs掺杂Ag基催化剂是一种高效的乙烯环氧化催化剂[ACS Catal. 11,3371 (2021)]. 然而,该工作是基于研究表面建模预测Ag基催化剂的性能,在实际反应过程中,Ag基催化剂是颗粒状的. 本文结合密度函数理论、Wulff构造理论和微观动力学分析来研究Ag基催化剂在颗粒模型上的催化性能. 研究表明,CuCs掺杂Ag基催化剂在选择性和活性方面都优于纯Ag基催化剂,这一点通过实验得到了证明. 进一步地表征分析发现,CuCs掺杂能促进颗粒的生长以及颗粒的分散,从而形成富含晶界的Ag颗粒. 此外,CuCs促进了催化剂表面亲电氧的形成,这均有利于环氧乙烷的形成和解吸. 本工作为理论与实验相结合的催化剂设计提供了一个案例研究.     

Highly efficient chirality inducers in nematic liquid crystals: synthesis of 7,7’-disubstituted 2,2’-methylenedioxy-1,1’-binaphthyls

ABSTRACT

We report the synthesis of 7,7?-disubstituted 2,2?-methylenedioxy-1,1?-binaphthyls and demonstrate their application as chiral dopants in the nematic mixture MLC-6260 to produce highly twisted cholesteric phases. Especially mesogenic and/or polarizable groups in the 7,7?-positions of the bridged binaphthyls generate unusually high helical twisting powers.     

Dopant induced morphologies of ZnS nanoparticles

We have reported the synthesis of cubic (zinc blende) phase ZnS: Ni²⁺ nanoparticles using a simple wet‐chemical method. Synthesized ZnS: Ni²⁺ nanoparticles had been characterized by X‐ray diffraction (XRD) and Energy Dispersive X‐ray (EDX) analysis. Surface morphologies were studied using Scanning Electron Microscopy (SEM). Fourier Transform Infrared (FTIR) spectra of selected samples were also carried out to confirm the presence of capping agent on the surface of the material. We have demonstrated that various morphologies like spherical, tetrapods, sheet and long‐armed multipods are emerged by simple chemical route without any vigorous reaction parameters and changing the concentration of dopant ions only. The probable mechanism for such morphologies has also been suggested.     

Model Studies of Rayleigh Instabilities via Microdesigned Interfaces

The energetic and kinetic properties of surfaces play a critical role in defining the microstructural changes that occur during sintering and high-temperature use of ceramics. Characterization of surface diffusion in ceramics is particularly difficult, and significant variations in reported values of surface diffusivities arise even in well-studied systems. Effects of impurities, surface energy anisotropy, and the onset of surface attachment limited kinetics (SALK) are believed to contribute to this variability. An overview of the use of Rayleigh instabilities as a means of characterizing surface diffusivities is presented. The development of models of morphological evolution that account for effects of surface energy anisotropy is reviewed, and the potential interplay between impurities and surface energy anisotropy is addressed. The status of experimental studies of Rayleigh instabilities in sapphire utilizing lithographically introduced pore channels of controlled geometry and crystallography is summarized. Results of model studies indicate that impurities can significantly influence both the spatial and temporal characteristics of Rayleigh instabilities; this is attributed at least in part to impurity effects on the surface energy anisotropy. Related model experiments indicate that the onset of SALK may also contribute significantly to apparent variations in surface diffusion coefficients.     

层状结构LiMn_(1-x)Cr_xO_2材料合成电化学性能研究

应用流变相法合成掺Cr层状结构锂锰氧化物.XRD分析显示,掺Cr后的锂锰氧化物为单斜晶系(Monoclinic)的层状化合物,而未掺Cr的产物结构则属斜方晶系(Orthorhombic).TEM观测表明,以上两种产物的颗粒都非常细小,直径在60300nm之间,呈球形,且分布均匀.作为锂离子电池正极材料,掺Cr产物的初始容量(>180mAh·g-1)远大于未掺杂的,室温下以50mA·g-1的速率充放40周后仍可保持94%的容量.电化学测试表明,掺Cr的锂锰氧化物能抑制层状结构进一步向尖晶石相转变,从而使其循环能够稳定在2.04.4V范围内.     

氯化银立方体微晶乳剂和{100}面扁平微晶乳剂的甲酸盐掺杂增感

将甲酸盐掺杂在乳剂微晶不同位置处,制备成氯化银立方体微晶乳剂和{100}面扁平微晶乳剂.实验发现:作为正空穴捕获剂,适当计量的甲酸盐在不增加乳剂灰雾的前提下,可使上述乳剂的感光度提升3—8倍.甲酸盐在两种晶形乳剂的不同位置掺杂的研究结果显示,甲酸盐均匀掺杂可比表面掺杂获得更高的感光度.在两种乳剂中甲酸盐掺杂增感都可与其后的硫增感、硫加金增感以及光谱增感协同作用,进一步提升乳剂的感光性能.     

Nd2O3添加量对BaTiO3陶瓷介电性能的影响

BaTiO₃ ceramics doped with Nd₂O₃(the additive content was respectively 0.001,0.002,0.003,0.005,0.01,0.03mol)were prepared by Sol-Gel method. Effects of Nd₂O₃ contents on the dielectric constant (ε), the dielectric loss (tanδ) ,the Curie-temperature (T_C) and the resistivity (ρ) of BaTiO₃ ceramic were studied. When Nd₂O₃ content was 0.001mol and 0.002mol, the dielectric constant was increased obviously, but the dielectric loss was also increased. When Nd₂O₃ content was 0.003mol, the dielectric constant was increased, and the dielectric loss was decreased, which was suitable for application in condenser. The resistivity was decreased obviously with the increasing of Nd₂O₃ contents, the resistivity was the smallest when Nd₂O₃ content was 0.001mol. The Curie-temperature was also decreased with the increasing of Nd₂O₃ contents.     

Defect microstructures of TiO2 rutile due to Zr dissolution and expulsion

Defect microstructure of Zr-dissolved TiO₂ polycrystals, homogenized as rutile structure at 1600 °C and then aged at 900 °C for 2-200 h in air, was characterized by analytical electron microscopy. Diffuse diffractions occurred at 1/2(211) as a result of Zr⁴⁺ substitution for Ti⁴⁺ with volume/charge compensating defect clusters. Upon annealing at 900 °C, plate-like Guinier and Preston (G.P.) zone appeared with the plate surface parallel to (100) and (010) and in association with dislocations. Commensurate superstructures with apparent triple {101} and {111} periodicity also occurred as metastable intermediates, which are presumably the precursor of the equilibrium ZrTi₂O₆ precipitate.     

稀土铕离子掺杂对拟薄水铝石晶体结构和相变的影响

研究了Eu3+离子对拟薄水铝石高温相变及微结构的影响。XRD及热分析结果表明,拟薄水铝石在560,882及1224℃分别经历-γAlOOH→-γAl2O3,γ-Al2O3→-θAl2O3和-θAl2O3→-αAl2O3相变。Eu3+掺杂后-γAlOOH→-γAl2O3相变温度不变,-γAl2O3→-θAl2O3和-θAl2O3→-αAl2O3相变温度分别提高到1054和1237℃。晶胞体积增大及衍射峰2θ值减小说明Eu3+离子以部分离子取代的形式进入-γAl2O3及-θAl2O3晶格。Eu3+离子进入晶格抑制了γ-Al2O3及-θAl2O3晶粒生长速率。-θAl2O3→-αAl2O3相变过程中Eu3+离子随Al3+一起迁移,并与Al3+离子及O2-离子形成了一个新生化合物相EuAl12O19。分析认为,该化合物在-αAl2O3晶界间存在,阻碍了-θAl2O3→-αAl2O3相转变过程中离子扩散速率,使-θAl2O3→-αAl2O3相变活化能由822.0提高到1063.15 kJ.mol-1。Eu3+离子掺杂使-θAl2O3→-αAl2O3相变过程由形核控制转变为表面扩散控制。     

Effect of Fe dopant on the physico-chemical and catalytic properties of vanadyl pyrophosphate catalysts

Summary 1% of Fe-doped and undoped vanadyl pyrophosphate catalysts were prepared via dihydrate method. The catalysts have been characterised by XRD, ICP, BET and SEM. The undoped catalyst was found to be more active and selective (77.6% selectivity at about 60 % conversion at 703 K).