Theoretical study on the catalytic properties of single-atom catalyst stabilised on silicon-doped graphene sheets

ABSTRACT

The stable configurations, electronic structures and catalytic activities of single-atom metal catalyst anchored silicon-doped graphene sheets (3Si-graphene-M, M?=?Ni and Pd) are investigated by using density functional theory calculations. Firstly, the adsorption stability and electronic property of different gas reactants (O₂, CO, 2CO, CO/O₂) on 3Si-graphene-M substrates are comparably analysed. It is found that the coadsorption of O₂/CO or 2CO molecules is more stable than that of the isolated O₂ or CO molecule. Meanwhile, the adsorbed species on 3Si-graphene-Ni sheet are more stable than those on the 3Si-graphene-Pd sheet. Secondly, the possible CO oxidation reactions on the 3Si-graphene-M are investigated through Eley–Rideal (ER), Langmuir–Hinshelwood (LH) and new termolecular Eley–Rideal (TER) mechanisms. Compared with the LH and TER mechanisms, the interaction between 2CO and O₂ molecules (O₂?+?CO → CO₃, CO₃?+?CO → 2CO₂) through ER reactions (< 0.2?eV) are an energetically more favourable. These results provide important reference for understanding the catalytic mechanism for CO oxidation on graphene-based catalyst.     

Glutathione-capped core-shell structured magnetite nanoparticles: Fabrication and their nonlinear optical characteristics

Core-shell structured magnetic Fe₃O₄@glutathione composite nanoparticles were synthesized and examined using diverse methods including Fourier-transform infrared spectroscopy, X-ray diffraction, energy-dispersive X-ray analysis, transmission electron microscope, thermogravimetric analysis, and vibrating sample magnetometer analysis. In addition, the nonlinear optical measurements were performed by both open and closed aperture z-scan methods using an aqueous colloidal solution of the fabricated nanoparticles. The colloidal system exhibited a positive nonlinear refractive index because of the self-focusing effect arising from optical re-orientation. Although optical re-orientation is a rare phenomenon in nanocolloids, high polarizability of the enveloping organic ligands caused optical re-orientation of the composite nanoparticles in the electrical field direction of the incident beam. Finally, the effect of external voltage on the nonlinear optical index was further investigated.     

四-(二甲氨基苯基)卟啉及其金属配合物的合成及光谱性能研究

以丙酸、乙酸、硝基苯为溶剂一步法合成了四-(二甲氨基苯基)卟啉(T(DMAP)P),并采用氯仿-N,N二甲基甲酰胺为溶剂合成了其与Zn2+,Mn2+,Tb3+三种离子的配合物,考察了溶剂种类、温度、时间对反应的影响,探讨了卟啉与金属盐反应两者用量的最佳比例,在较温和条件下合成了卟啉金属配合物,避免了高温合成金属卟啉不稳定现象。利用元素分析,IR,UV-Vis等方法确定了目标化合物的组成和结构。考察了不同浓度及温度下卟啉配合物的电导率并计算了其摩尔电导率。实验结果发现,卟啉与铽离子配合物摩尔电导率远大于锌、锰配合物。实验研究了不同金属离子对反应的影响,重点考察了卟啉及其金属配合物的分子光谱性能的差异。与四苯基卟啉相比,T(DMAP)P及其金属配合物UV-Vis光谱均发生红移,探讨了该现象产生的原因。     

Effect of pH value on the structural and magnetic properties of nanocrystalline strontium hexaferrite thin films

Strontium hexaferrite SrFe₁₂O₁₉ thin films have been synthesized at different pH, adjusted by NH₄OH, on the Si (1 0 0) substrate using a spin coating sol-gel process. Fourier transform infrared spectroscopy analysis and theoretical calculations were conducted for determination and controlling metal citrates in solution precursors. X-ray diffraction, scanning electron microscopy and vibrating sample magnetometer were applied to evaluate the composition, microstructure, crystallite size and magnetic properties of the SrFe₁₂O₁₉ thin films. Using the solution with pH 7, the approximately single phase strontium hexaferrite thin films with optimum physical properties can be obtained at calcination temperature of 800 °C. The SrFe₁₂O₁₉ thin films derived from the solution with pH 7 after calcination at 800 °C exhibited crystallite size of 42 nm and magnetic properties of M_s=267 emu/cm³ (at 10 kOe), M_r=134 emu/cm³ and H_c=4290 Oe.     

Microstructure evolution and mechanical property of pulsed laser welded Ni-based superalloy

For evaluating the microstructure evolution and mechanical property of Ni-based Hastelloy C-276 weld joint by the pulsed laser welding, the influence of pulsed laser welding on the microstructure and mechanical property of the weld joint is investigated by the analysis of the microstructure morphology, microhardness, phase structure and tensile property. The results indicate that, in the fusion zone three sections are divided on the basis of the patterns of grain structures. In the weld joint, the element segregation is found, but the trend of brittle phase׳s formation is weakened. The weld microhardness presents just a little higher than that of base metal, and there is no obvious the softened heat affected zone. Meanwhile in the weld joint, the phase structure is still the face-center cubic with the tiny shift of peak positions and widened Full Width at Half-Maximum. The yield strength of weld joint is the same as that of base metal, and the tensile strength is nearly 90% of that of base metal. The decreased tensile strength is mainly attributed to the dislocation piling-up.     

k（k〉2）光子Jaynes—Cummings模型中自发辐射场的位相演化特性

应用Ｐｅｇｇ－Ｂａｒｎｅｔ（ＰＢ）位相理论，研究了ｋ光子Ｊａｙｎｅｓ－Ｃｕｍｍｉｎｇｓ（Ｊ－Ｃ）模型中自发辐射场的位相演化特性，计算了辐射场的位相几率分布函数与位相涨落，给出了在极坐标中位相几率分布演化曲线。     

强一致收敛下的初值敏感性与等度连续性

首先,举例指出了《Nonlinear Anglgsis》文中定理3.2的条件下并不能使函数序列的初值敏感性遗传至极限函数,并证明了若函数序列的敏感常数的上极限为某一正数,则在强一致收敛下,函数序列的极限函数也具有初值敏感性.其次,证明了在强一致收敛下,序列系统的等度连续性和一致几乎周期性能被极限系统所继承.     

扫描近场光学显微镜中两类光纤探针传输特性的研究

采用局域模式耦合理论，对扫描近场光学显微镜中的两类光纤探针－腐蚀锥和熔拉锥的传输特性进行了比较和分析。给出了光在探针锥中传输时耦合效率的分布情况，以及传输效率随锥长，针尖直径和光波长变化的特性。     

Electronic structure and magnetism in full-Heusler compound Mn2ZnGe

The first-principle calculations within density functional theory are used to investigate the electronic structure and magnetism of the Mn₂ZnGe Heusler alloy with CuHg₂Ti-type structure. The half-metallic ferrimagnets (HMFs) in Mn₂ZnGe are predicted. The energy gap lies in the minority-spin band for the Mn₂ZnGe alloy. The calculated total spin magnetic moment is −2μ_B per unit cell for Mn₂ZnGe alloy, the magnetic moments of Zn and Mn(B) are antiparallel to that of Mn(A), and we also found that the half-metallic properties of Mn₂ZnGe are insensitive to the dependence of lattice within the wide range of 5.69 and 5.80 Å where exhibiting perfect 100% spin polarization at the Fermi energy.