四氧化三锰的制备及其对奥克托今的热分解行为研究

以氯化锰为锰源、六次甲基四胺(HMT)为沉淀剂,采用均相沉淀法在90℃制备了Mn3O4,用X-射线衍射、扫描电镜和透射电镜等对产物的结构和形貌进行表征,利用DSC技术研究了产物对奥克托今(HMX)的热分解行为的影响。结果表明,制备产物为四方结构Mn3O4,直径约为300 nm的近似球形。Mn3O4的加入,对HMX的分解峰形变化不大,但分解温度增大,分解活化能增加。     

甲醇在Fe/MgO、Co/MgO和Ni/MgO催化剂上裂解制备氢气

采用浸渍法制备出3种MgO负载型过渡金属催化剂Fe/MgO、Co/MgO和Ni/MgO,系统研究了甲醇在3种催化剂上于600℃下的裂解产物。结果表明,3种催化剂均能催化甲醇裂解产生富氢气体,同时产生碳纳米管。其中,Ni/MgO具有最佳的催化效果。     

四氧化三锰的简易制备及其作为电池阳极材料的电化学性能研究

在90℃下,采用空气氧化法于弱碱性介质中氧化Mn2+制备Mn3O4。X-射线衍射和扫描电镜表明,产物为四方结构的Mn3O4,纯度高、结晶良好,具有近似球形形貌。电化学测试结果表明,在50 mA/g的电流密度下,Mn3O4作为阳极材料的初始放电容量为198 mA.h/g。在不同电流密度下循环50次后,放电容量基本可以回到初始值。     

N,N’-二四唑胺过渡金属配合物M（BTA）（H_2O）_n对RDX和HMX热分解行为的影响

利用DSC技术研究了5种N,N’-二四唑胺过渡金属配合物MBTA（H2O）n（M=Mn、Co,n=4;M=Ni,n=3;M=Zn,n=3.5;M=Pb,n=2;BTA2-=N,N’-二四唑离子）对RDX和HMX热分解行为的影响,从分解峰温、热爆炸临界温度等特征参数评价了配合物对RDX和HMX热分解行为的影响效果。     

含能配合物M(BTA)(bpy)_m·nH_2O的合成及液相生成反应热动力学研究

室温下合成了6种未见报道的固态含能配合物M(BTA)(bpy)m.nH2O(M=Mn,m=1,n=1;M=Co,m=2,n=5;M=Ni,m=2,n=6;M=Cu,m=2,n=0;M=Zn,m=2,n=1;M=Pb,m=1,n=0;BTA=N,N’-二四唑胺离子,bpy=2,2’-联吡啶),对它们进行了组成、红外光谱、密度等表征。测定了298.15 K下各配合物的液相生成反应焓变△rHmθ,改变液相反应温度,在实验和计算基础上,得到了液相生成反应的热力学参数(活化焓△Hθ≠、活化熵△S≠θ和活化自由能△Gθ≠)、速率常数k和动力学参数(表现活化能E、频率因子ln[A/s]和反应级数n)。     

N,N’-二四唑胺过渡金属配合物M（BTA）（H2O）n对RDX和HMX热分解行为的影响

利用DSC技术研究了5种N,N’-二四唑胺过渡金属配合物MBTA(H2O)n(M=Mn、Co,n=4;M=Ni,n=3;M=Zn,n=3.5;M=Pb,n=2;BTA2-=N,N’-二四唑离子)对RDX和HMX热分解行为的影响,从分解峰温、热爆炸临界温度等特征参数评价了配合物对RDX和HMX热分解行为的影响效果。     

N,N'-二四唑胺和邻菲啰啉与碱土金属钙、锶混配配合物的合成与表征

以N,N’－二四唑胺（C2H3N9）和邻菲哕啉（C12H8N2）为配体合成碱土金属Ca,Sr的含能配合物,并对配合物进行了基础的物化表征。化学分析和元素分析确定配合物的组成为Ca（C2HN9）（C12H8N2）：（H2O）。（1）和Sr（C2HN9）（C12H8N2）2（H2O）2（2）。溶解性实验表明,常温下配合物难溶于水加热时溶解,且不溶于甲醇、乙腈等有机溶剂。红外光谱分析表明,配体邻菲啰啉以双齿螯合形式与中心离子配位,配体N,N’－二四唑胺中N原子参与了配位。TG—DTG热分析显示配合物在氮气气氛、研究温度范围内有三个热分解过程,最终分解产物可能分别为以CaO与SrO为主的混合物。     

Thermochemistry of Ternary Complex Dy(Et_2dtc)_3(phen)

The ternary solid complex was synthesized with sodium diethyldithiocarbamate (NaEt2dtc), 1,10-phenanthroline (phen) and low hydrated dysprosium chloride in absolute ethanol by improved method of reference. The title complex was identified as the general formula of Dy(Et2dtc)3(phen) by chemical and elemental analyses. IR spectrum of the complex shows that the Dy3 coordinated with six sulfur atoms of three NaEt2dtc and two nitrogen atoms of phen. It is assumed that the coordination number of Dy3 is eight.The enthalpy change of liquid-phase reaction of formation, ΔrHθm(l), is determined as (-19.091±0.015) kJ·mol-1 at 298.15 K by a microcalorimeter, and the enthalpy change of the solid-phase reaction of formation, ΔrHθm(s), is calculated as (139.641±0.482) kJ·mol-1 on the basis of a thermochemical cycle. The thermodynamic of reaction of formation was studied by changing the temperature of liquid-phase reaction. The constant-volume combustion energy of the complex, ΔcU, is determined as (-16730.21±9.25) kJ·mol-1 by a precise rotating-bomb calorimeter at 298.15 K. Its standard enthalpies of combustion, ΔcHθm, and standard enthalpies of formation, ΔfHθm, are calculated as (-16749.42±9.25) kJ·mol-1 and (-2019.68±10.19) kJ·mol-1, respectively.     

锂离子电池负极材料Fe_2O_3/石墨复合材料的水热合成和电化学性能研究

在230℃,利用水热法将纳米氧化铁担载于石墨上制备了Fe2O3/石墨复合材料,运用X射线衍射和扫描电镜对其形貌和结构进行了表征,并研究了目标物作为锂离子电池负极材料的电化学储锂性能。研究结果证明,经50次循环后,复合材料的嵌锂容量维持在425mAh/g,远高于相同条件下石墨的252mAh/g和Fe2O3的108mAh/g。     

Thermochemistry on Coordination Behavior of Neodymium Chloride Hydrate with Diethylammonium Diethyldithiocarbamate

The complex of neodymium chloride lower hydrate with diethylammonium diethyldithiocarbamate (D-DDC) was synthesized conveniently in absolute alcohol and dry N2 atmosphere. The title complex was identified as Et2NH2 [ Nd(S2CNEt2)4] by chemical and elemental analyses and the bonding characteristics of which was characterized by IR. The enthalpies of solution of neodymium chloride hydrate and D-DDC in absolute alcohol at 298.15 K and the enthalpies change of liquid-phase reaction of formation for Et2NH2[ Nd (S2CNEt2)4] at different temperatures were determined by microealorimetry. On the basis of experimental and calculated results, three thermodynamic parameters (the activation enthalpy, the activation entropy and the activation free energy), the rate constant and three kinetic parameters (the apparent activation energy, the pre-exponential constant and the reaction order) of liquid-phase reaction of formation were obtained.The enthalpy change of the solid-phase title reaction at 298.15 K was calculated by a thermochemical cycle.