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.     

SAPO-34提升铁钒基催化剂抗碱性能研究

采用浸渍法制备Fe-VO_x/SAPO-34和Fe-VO_x/TiO₂脱硝催化剂,探究SAPO-34分子筛与TiO₂两种载体负载铁钒基氧化物催化活性及抗碱性能的差异。借助X射线衍射(XRD)、X射线光电子能谱(XPS)、氨气程序升温脱附(NH₃-TPD)、氢气程序升温还原(H₂-TPR)、原位红外漫反射(in-situ DRIFTs)等表征手段对催化剂的骨架结构、表面物化性质、氧化还原能力以及对反应气体的吸脱附情况进行分析。结果表明:SAPO-34分子筛内部特定的孔道结构和稳定的骨架,有利于活性组分在载体上均匀分散,降低碱金属对表面活性中心的物理覆盖作用;同时其表面丰富的酸位点能够作为碱金属捕获位,保护催化剂表面的活性中心,保证催化剂的吸附-反应过程能够正常进行,从而使Fe-VO_x/SAPO-34表现出良好的抗碱金属能力。     

Terahertz Dual-Band Near-Zero Effective Index Metamaterial Based on Double-Sided Metal Microstructure

Journal of Russian Laser Research - The zero-refractive-index metamaterials have excellent electromagnetic properties, which provide new ideas and methods to realize the control of electromagnetic...     

Differential Entropy of Induced Random State Ensemble

International Journal of Theoretical Physics - In this paper, we will consider the exact calculation of differential entropy of induced random state ensemble by partial tracing a subsystem over...     

利用空间位阻和氢溢流协同作用促进5-羟甲基糠醛选择性加氢制备5-甲基糠醛

化学工业生产中，用氢气为还原剂，通过选择性加氢可以制备多种重要化学品。5-羟甲基糠醛是重要的生物质基平台化合物，而5-甲基糠醛是用途广泛的化学品。由5-羟甲基糠醛加氢得到5-甲基糠醛是一条非常理想的路径，但是选择性活化C-OH非常困难。本文设计并制备了Pt@PVP/Nb₂O₅(PVP: 聚乙烯吡咯烷酮)催化剂，该催化体系巧妙地结合了位阻效应、氢溢流和催化剂界面的电子效应，系统研究了该催化剂对5-羟甲基糠醛选择性加氢制备5-甲基糠醛催化性能，在最优条件下，5-甲基糠醛的选择性可达92%。利用密度泛函理论计算研究了5-羟甲基糠醛选择性加氢制备5-甲基糠醛反应路径。     

Mechanistic Investigation and Conductance Modulation of a Metal-Molecule-Metal Junction via Extra Acid Addition

One important prerequisite for the fabrication of molecular functional device strongly relies on the understanding the conducting behaviors of the metal-molecule-metal junction that can respond to an external stimulus. The model Lewis basic molecule 4,4′-(pyridine-3,5-diyl)dibenzonitrile (DBP), which can react with Lewis acid and protic acid, was synthesized. Then, the molecular conducting behavior of DBP, DBP-B(C₆F₅)₃, and DBP-TfOH (DBP-B(C₆F₅)₃, and DBP-TfOH were produced by Lewis acid and protonic acid treatment of DBP) was researched and compared. Given that their identical physical paths for DBP, DBP-B(C₆F₅)₃, and DBP-TfOH to sustain charge transport, our results indicate that modifying the molecular electronic structure, even not directly changing the conductive physical backbone, can tune the charge transporting ability by nearly one order of magnitude. Furthermore, the addition of another Lewis base triethylamine (of stronger alkaline than DBP), to Lewis acid-base pair reverts the electrical properties back to that of a single DBP junction, that is constructive to propose a useful but simple strategy for the design and construction of reversible and controllable molecular device based on pyridine derived molecule.     

Heterostructured MoS2/GPC anode: the synergistic lithium storage performance and lithiation kinetics

Journal of Solid State Electrochemistry - Grapefruit peel carbon (GPC) is prepared from waste grapefruit peel and further used as substrate for in situ construction of MoS2 arrays, forming MoS2/GPC...     

中空介孔SiO2纳米球的制备、改性及其对Al3+荧光识别研究

中空介孔SiO2由于中空多孔的结构而常用作功能材料的基底.将中空介孔SiO2进行官能团修饰,并应用为荧光传感材料是中空介孔SiO2一个重要的研究领域.本论文采用聚丙烯酸(PAA)为中空模板,聚醚F127为造孔剂,正硅酸乙酯(TEOS)为硅源,氨水为催化剂在乙醇体系中制备了中空介孔SiO2纳米球.系统研究了搅拌速度和聚醚F127引入量对中空介孔SiO2纳米球形貌及比表面积的影响.通过透射电镜、N2-等温吸附脱附曲线等表征说明该合成方法具有很好的普适性,通过调节F127的引入可以实现对比表面积的有效控制.通过氨基化、席夫碱反应进行荧光修饰,进一步研究表明荧光修饰后的中空介孔SiO2纳米球在水溶液中能够实现对Al3+的有效检测,检测限为1.19×10 -7M.