Chelating Metal Ions in a Metal-Organic Framework for Constructing a Biomimetic Catalyst Through Post-modification

Crystal engineering, as a burgeoning technology, has been widely used to construct metalloporphyrins biomimetic catalysts. Herein, a bimetallic metal-organic framework (MOF) was constructed by 4-(4-carboxyphenyl)-1,2,4-triazole ligand, Co²⁺ and Zr⁴⁺ metal ions by solvothermal reaction(named PFC-88). A N,N-chelation site was found between the two adjacent ligands in PFC-88, consequently a porphyrin-like structure was obtained through chelating Fe³⁺ in this site by post-modification, named PFC-88-Fe. The result of a single crystal X-ray technology verified that Fe ions were successfully metalated in the N,N-chelation site of PFC-88, which is assisted by the X-ray absorption near-edge structure(XANES) spectra. An o-phenylenediamine oxidation reaction was applied to assessing the catalytic activity of PFC-88-Fe, in which the absorbance increases of phenazine-2,3-diamine at λ=418 nm were recorded by absorption spectroscopy in kinetic mode, exhibiting the application potential as a biomimetic catalyst.     

Green synthesis and characterization of Tb-Fe-O-Cu ceramic nanocomposite and its application in simultaneous electrochemical sensing of zinc,cadmium and lead

In this work, a green technique for preparing TbFeO₃/CuO was reported by employing Crataegus and Lantana Camara leaves as fuel and alkalizing agents, respectively. The new sensor based on the perovskite-type nanocomposite was employed as a sensitive and selective platform to detect Pb(II), Zn(II) and Cd(II) simultaneously. TbFeO₃/CuO/Carbon paste electrode (CPE) exhibited a large specific surface area and great electrical conductivity, which enhanced electron transport in the electrochemical process considerably. Moreover, square wave anodic stripping voltammetry (SWASV) was used for the investigation of some factors influencing the sensor sensitivity like pH, modifier concentration, as well as accumulation time and potential. Therefore, the low detection limit (LOD) and a wide linear range were obtained at optimum conditions. In this study, a linear range between 0.9 and 110 µg/L for three ions and LOD of 0.48, 0.29 and 0.12 for zinc, cadmium and lead were achieved, respectively. Moreover, TbFeO₃/CuO/CPE was employed to detect zinc, cadmium and lead ions simultaneously in the real samples so that the results have shown consistency with a standard inductively coupled plasma (ICP).     

以磷化铁为添加剂沿(111)面生长磷掺杂金刚石大单晶

掺杂是调控金刚石性能的一种重要手段。本文采用温度梯度法,在5.6 GPa、1 312 ℃的条件下,选用Fe₃P作为磷源进行磷掺杂金刚石大单晶的合成。金刚石样品的显微光学照片表明,随着Fe₃P添加比例的增加,金刚石晶体的颜色逐渐变深,包裹体数量逐渐增加,晶形由板状转变为塔状直至骸晶。金刚石晶形的变化表明Fe₃P的添加使生长金刚石的V形区向右偏移,这是Fe₃P改变触媒特性的缘故。红外光谱分析表明,Fe₃P的添加使金刚石晶体中氮含量上升,这说明磷的进入诱使氮原子更容易进入金刚石晶格中。激光拉曼光谱测试表明,随着Fe₃P添加比例的增加,所合成的掺磷金刚石的拉曼峰位变化不大,其半峰全宽(FWHM)值变大,这说明磷的进入使得金刚石晶格畸变增加。XPS测试结果显示,随着Fe₃P添加比例的增加,金刚石晶体中磷相对碳的原子百分含量也会增加,这意味着添加Fe₃P所合成的金刚石晶体中有磷存在。     

Electrochemical sensing of H2O2 using cobalt oxide modified TiO2 nanotubes

Cobalt oxide (Co₃O₄) modified anatase titanium dioxide nanotubes (ATNTs) have been investigated for the electrochemical sensing of hydrogen peroxide (H₂O₂). ATNTs have been synthesized by a two-step anodization process. ATNTs were then modified with Co₃O₄ employing chemical bath deposition method. The structure and morphology of ATNTs and their modification with Co₃O₄ has been confirmed by X-ray diffraction by scanning electron microscopy. H₂O₂ sensing has been studied in 0.1 M PBS solution, by cyclic voltammetry and amperometry. Variation in the peak positions and current densities was observed with addition of H₂O₂ for Co₃O₄ modified ATNTs. Sensitivity and limit of detection improved with modification of ATNTs with Co₃O₄ with precursor concentration up to 0.8 M. However, at higher precursor concentrations sensitivity and limit of detection toward H₂O₂ deteriorated. Co₃O₄ Modified ATNTS using 0.8 M precursor concentration are comparatively more suitable for H₂O₂ sensing applications due to the optimum formation of Co₃O₄/ATNTs heterojunctions.     

Terahertz generation in quantum cascade structures by two-color deriving fields: An approach to reach inversion population via optical pumping

In this paper, a quantum cascade laser (QCL) design is proposed based on GaAs/AlGaAs material system, which simultaneously operates at three widely separated wavelengths (${\lambda }_1=11.1\mu m,{\lambda }_2=14.1\mu m$ and ${\lambda }_{THz}=60\mu m$). In the design, all the wavelength radiations are achieved by the engineering of the electronic spectrum via the quantum-well widths and the applied electric field in a single active region within a same waveguide. The mid-infrared (mid-IR) wavelengths are obtained by adoption a dual-upper-state active region, and the proposed design aims to use both the mid-IR radiations as the coherent deriving fields to populate the upper THz lasing state to aid the THz-laser population inversion via optical pumping instead of direct electrical injection. A detailed analysis of electronic transport in the structure is carried out using a multi-level rate-equation model. The results show that the proposed structure offers an alternative approach to room temperature THz generation in QCLs.     

材料表征方法理论与实践课程的改革与建设*

通过与超星专业慕课制作团队合作搭建网络教学平台,将线上慕课教学与线下实验教学相结合,对材料表征方法理论与实践课程进行了全方位的改革。与传统实验教学相比,改革后的课程不仅能够激发学生的学习兴趣,实现时间空间的相对自由,还可以完善考核机制,提升教学质量,从而为高校化学研究生实验课程的改革提供一定的借鉴意义。     

Application of advanced nuclear analytical techniques for the electrocatalyst's characterization: Paving the path for mechanistic investigations

As the application of electrocatalyst continues to expand, envisaging the hidden mechanisms occurring at various length scale affecting the catalytic efficiency became important. To enhance the stability of electrocatalyst and reduce the cost, it is of paramount importance to reveal the active site's dynamics (using in situ techniques for getting the real-time information) which directly affect the reactions such as oxygen evolution reaction, hydrogen evolution reaction, and so on. Since such reactions are crucial for many engineering and scientific applications, in situ characterization techniques are required, which could capture such reactions happening at a different length and time scale. This article analyzes the recent progress made in the field of electrocatalyst's characterization using in situ neutron techniques. The article also paves the future path and has delineated the future challenges involved in multiscale correlative techniques (e.g., neutron techniques in the combination of synchrotron or microscopic techniques) used for getting the multiscale (atomic to micrometer range) mechanistic information about the electrocatalyst's working and degradation.     

1,3,5-三(羧基甲氧基)苯镍配位聚合物的合成、晶体结构及性质研究

采用溶剂热法,1,3,5-三(羧基甲氧基)苯为定向配体和乙酸镍反应构筑了一个新型的金属配位聚合物[Ni(TB)₂(H₂O)₂]_n·2H₂O,其中H₃TB=1,3,5-三(羧基甲氧基)苯,通过元素分析、IR及X射线单晶衍射对配合物结构进行表征,并研究其荧光性质、热稳定性及Hirshfeld表面作用力。单晶结构分析表明,该配合物属于三斜晶系,空间群$P \overline{1}$,配合物中心离子Ni(Ⅱ)分别与来自两个水分子上的氧原子及四个不同1,3,5-三(羧基甲氧基)苯配体的羧酸氧原子配位,形成六配位的NiO₆八面体构型,并通过与1,3,5-三(羧基甲氧基)苯配体的氧原子配位不断延伸形成具有孔洞结构的一维链状构型。配合物具有良好的荧光性能和热稳定性。Hirshfeld表面作用分析表明配合物分子中O…H/H…O作用占主导且占比为39.0%,而H…H的作用力占比为25.9%,O…O的作用力占比为13.6%。     

Synthesis of flower-like WS2 by chemical vapor deposition

Flower-like tungsten disulfide (WS₂) with a diameter of 5-10 μm is prepared by chemical vapor deposition (CVD). Scanning electron microscopy (SEM), energy dispersive spectrometer (EDS), Raman spectroscopy, and ultraviolet-visible (UV-vis) spectroscopy are used to characterize its morphological and optical properties, and its growth mechanism is discussed. The key factors for the formation of flower-like WS₂ are determined. Firstly, the cooling process causes the generation of nucleation dislocations, and then the "leaf" growth of flower-like WS₂ is achieved by increasing the temperature.