三维无溶剂含能Ag-MOF的制备、热分解动力学及爆炸性能

Solvent molecules can significantly reduce the heat of detonation and stability of energetic metal-organic framework (EMOF) materials, and the development of solvent-free EMOFs has become an effective strategy to prepare high-energy density materials. In this study, a solvent-free EMOF, [Ag₂(DTPZ)]_n (1) (N% = 32.58%), was synthesized by reacting a high-energy ligand, 2, 3-di(1H-tetrazol-5-yl)pyrazine (H₂DTPZ), with silver ions under hydrothermal conditions, and it was structurally characterized by elemental analysis, infrared spectroscopy, X-ray diffraction, and thermal analysis. In 1, the DTPZ²⁻ ligands that adopted a highly torsional configuration bridged the Ag⁺ ions in an octadentate coordination mode to form a three-dimensional framework (ρ = 2.812 g∙cm⁻³). The large steric effect and strong coordination ability of DTPZ²⁻ effectively prevented the solvent molecules from binding with the metal centers or occupying the voids of 1. Moreover, the strong π-π stacking interactions [centroid-centroid distance = 0.34461(1) nm] between the tetrazole rings in different DTPZ²⁻ ligands provided a high thermal stability to the framework (T_e = 619.1 K, T_p = 658.7 K). Thermal analysis showed that a one-step rapid weight loss with intense heat release primarily occurred during the decomposition of 1, suggesting potential energetic characteristics. Non-isothermal thermokinetic analyses (based on the Kissinger and Ozawa-Doyle methods) were performed using differential scanning calorimetry to obtain the thermoanalysis kinetic parameters of the thermodecomposition of 1 (E_a = 272.1 kJ·mol⁻¹, E_o = 268.9 kJ·mol⁻¹; lgA =19.67 s⁻¹). The related thermodynamic parameters [enthalpy of activation (ΔH^≠ = 266.9 kJ·mol⁻¹), entropy of activation (ΔS^≠ = 125.4 J·mol⁻¹·K⁻¹), free energy of activation (ΔG^≠ = 188.3 kJ·mol⁻¹)], critical temperature of thermal explosion (T_b = 607.1 K), and self-accelerating decomposition temperature (T_SADT = 595.8 K) of the decomposition reaction were also calculated based on the decomposition peak temperature and extrapolated onset temperature when the heating rate approached zero. The results revealed that 1 featured good thermal safety, and its decomposition was a non-spontaneous entropy-driven process. The standard molar enthalpy for the formation of 1 was calculated to be (2165.99 ± 0.81) kJ·mol⁻¹ based on its constant volume combustion energy determined using a precise rotating oxygen bomb calorimeter. Detonation and safety performance tests revealed that 1 was insensitive to impact and friction, and its heat of detonation (10.15 kJ·g⁻¹) was higher than that of common ammonium nitrate explosives, such as octogen (HMX), hexogene (RDX), and 2, 4, 6-trinitrotoluene (TNT), indicating that 1 is a promising high-energy and insensitive material.     

咪唑-氰基合铁(Ⅲ)氢键型超分子晶体的合成、相变及介电性质

通过溶剂蒸发法,咪唑、18-冠醚-6和铁氰酸在甲醇溶液内反应,获得了氰基合铁配合物氢键型笼状超分子晶体材料(C3H5N2)3[Fe(CN)6]·2(18-crown-6)·2H2O(1)。通过变温X射线单晶衍射、红外光谱、元素分析、热重分析(TG)、差示扫描量热法(DSC)和变温-介电常数测试等对该晶体进行了结构、热能及电性能分析。该晶体的空间群为P21/c,属于单斜晶系,结构显示氰基合铁阳离子、水分子和咪唑阳离子在空间内通过氢键的相互作用形成以铁原子为顶点的三维笼状结构。温度变化触发笼状结构突变,同时引起[Fe(CN)6]3-框架内超分子发生动态摆动,从而引起晶体结构发生相变,该结构相变温度区间伴随介电物理特性阶梯状变化,从220到280 K,介电常数由38变为43,且可逆。温度在270 K之后的介电突然跃升是水汽影响导致。     

Hydrothermal Synthesis and Structural Characterization of a Novel 3-D Open Framework Zinc Phosphate Microporous Compound(C_5N_2H_(14))·[Zn_3(OH_2)(PO_4)_2(HPO_4)]

One novel organically templated zincophophate(C5N2H14)·[Zn3(OH2)(PO4)2(HPO4)] has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction together with elemental analysis, infrared spectroscopy, thermogravimetric analysis, and powder X-ray diffraction. The title compound crystallizes in the monoclinic space group P21/n, with a = 9.7904(11), b = 14.0287(14), c = 11.8651(13) , β = 104.690(3), V = 1576.4(3) 3, Z = 4, T = 296(2) K, Mr = 601.31 and Dc = 2.533 g/cm3. The compound consists of a macroanionic [Zn3(OH2)(PO4)2(HPO4)]2- framework and(C5N2H14)2+ cations, and its structure is built up from ZnO3(OH2), ZnO4, HPO4 and PO4 tetrahedral units that result in 4, 8 and 10-ring channels.     

表面配位金属-有机框架薄膜的制备及电催化应用

设计和开发高效电催化剂对能源的存储和转化具有十分重要的意义。金属-有机框架(MOF)在基底表面通过液相外延层层配位组装的MOF薄膜(也被称作表面配位MOF薄膜,SURMOF)具有厚度可调节、生长取向可控以及表面均匀致密等优点,在电催化反应领域得到了广泛的研究和应用。本文总结了SURMOF及其衍生薄膜(SURMOF-D)的制备及其在电催化应用中的研究进展。由于SURMOF及其衍生薄膜具有结构多样性和功能可调节性,可在析氧反应、析氢反应、氧化还原反应、二氧化碳还原反应、超级电容器和串联电催化等过程中提供丰富的活性位点并加速电荷转移,使电催化性能更加高效。本文还讨论了SURMOF作为一类新型的薄膜催化剂在电催化应用中的研究挑战和存在的问题。     

机载多框架光电吊舱两级隔振设计

在分析了目前常用的机载光电设备隔振系统的基础上,针对两轴四框架的结构特点,提出了一种基于多框架的两级隔振方案,克服了目前隔振系统体积、重量大,加工装配要求高的缺点。基于隔振模型的理论计算表明,根据系统给定的质量比和频率比,优化选择内外框架的刚度比,即选择合适的内外框隔振器可达到理想的隔振效果。通过某型光电吊舱的扫频实验...     

Σ_e~n(n≥2)型Banach空间上的摄动类问题

深化对本性谱的认识;给出∑_e~n(n≥2)型Banach空间上的摄动类问题的反面回答.     

数学教学设计的新视角——基于知识心理发生的探讨

对于数学知识发生的心理过程,我们只能近似地描述:主体已经先在地(经过学习,或先天赋予)掌握了不少数学知识,这些知识已经不同于外在的、存储在书本上的知识,它们经由意识结构的机能作用,被赋予了人的精神的印记,就是意识状态或精神状态的世界,或关于行为意向的世界中的知识,即意识机能中的处于待命状态,随时都可以被调用的     

上三角算子矩阵的谱

设X,y是Banach空间,对A∈B(X),B∈B(y),C∈B(Y,X),以M_C记X⊕Y上的算子(ACOB).本文给出了算子M_C的20种谱的结构表示,18种谱的填洞性质以及关于这些问题的有趣例子.     

随机迭代算法的几乎必然T-稳定性及收敛性

目的是在可分Banach空间的框架下,研究某些类型的-弱压缩型的随机算子的Ishikawa-型及Mann-型随机迭代算法的几乎必然T-稳定性及收敛性.在适当的条件下,证明了该类随机算子的随机不动点的Bochner可积性以及这两类随机迭代算法的几乎必然T-稳定性及收敛性.     

反Banach空间内涉及广义混合似臣分不等式问题的双水平广义混合平衡问题

在自反Banach空间内,引入和研究了一类新的涉及广义混合似变分不等式问题的双水平广义混合平衡问题(BGMEP).首先,为了计算BGMEP的近似解,引入了一类辅助广义混合平衡问题(AGMEP).由使用一极小极大不等式,在没有任何强制条件的相当温和假设下,证明了AGMEP解的存在性和唯一性.利用辅助原理技巧,建议和分析了一类计算BGMEP的近似解的新迭代算法.在没有任何强制条件的相当温和假设下,证明了由算法生成的迭代序列的强收敛性.这些结果是新的并且推广了这一领域内某些最近结果.