钛酸锌的制备及其对高氯酸铵热分解的催化性能

ZnTiO₃ nanocrystals were prepared by sol-gel method, using Zn(NO₃)₂ and Ti(C₄H₉O)₄ in the topic. The as-prepared ZnTiO₃ nanocrystals were characterized by XRD, FTIR and TEM, and the catalytic performance of ZnTiO₃ nanocrystals of different contents for the ammonium perchlorate(AP)decomposition was investigated by thermal analysis. The results indicate that ZnTiO₃ with pure cube structure can be synthesized at 600 ℃ by this procedure,which was spheroid with particle size of about 60~100 nm. The results expressed that the low temperature decomposition peaks of AP is advanced by 17 ℃ and the high temperature decomposition peaks of AP is advanced by 24 ℃ when adding 5% nanoparticle ZnTiO₃ powder. The catalytic effects of ZnTiO₃ powders on the high temperature decomposition of AP are less than that of nanometer metal powders, but all the micron metal powders decrease the low decomposition temperature of AP.     

Y2O3纳米粒子/碳纳米管复合体的制备及其催化高氯酸铵热分解

采用化学液相沉淀法制备Y2O3纳米粒子/碳纳米管复合体(Y2O3/CNTC),利用扫描电镜(SEM)和X 射线光电子能谱(XPS)对其结构和成分进行了表征. 结果表明, Y2O3纳米粒子能负载在碳纳米管上,且负载效果较好. 采用差热分析研究了Y2O3/CNTC 对高氯酸铵热分解的催化性能, 结果表明, Y2O3 /CNTC 可显著降低高氯酸铵(AP)的高温分解峰温,表现出对AP 高温分解良好的催化性能. 相同量的Y2O3/CNTC 和纯Y2O3纳米粒子进行对比, Y2O3 /CNTC表现出更强的催化性能.当Y2O3/CNTC的质量分数为4%时,使AP的高温分解峰温提前131.14C[deg].     

A review on the use of nanometals as catalysts for the thermal decomposition of ammonium perchlorate

In this review, an attempt to collect summarized literature data on catalytic effect of nanosized metals and nanoalloys on the thermal decomposition of ammonium perchlorates (AP) is made. Several experimental results show nanometals are more effective catalysts as compared to nanosized metal oxides. During decomposition process; metal react with oxygen containing species that are produced in decomposition process; and metal oxide is formed with large amount of heat which enhances the catalytic activity of metals as compared to metal oxide nanoparticles.     

Mg2NiH4对高氯酸铵热分解过程的影响

采用置换-扩散法制备了储氢材料Mg2NiH4, 用XRD, ICP和DSC-TG方法对其结构进行了表征. 用热分析法(DSC)研究了Mg2NiH4对高氯酸铵(AP)热分解过程的影响. 研究结果表明, Mg2NiH4对AP热分解过程有较大影响. Mg2NiH4可以显著促进AP的低温热分解过程, 降低高温热分解温度, 使DSC表观分解热明显增大. 随着加入量的增加, Mg2NiH4对AP热分解的催化促进作用增强, 当Mg2NiH4加入的质量分数为30％时, DSC表观分解热最大. 吸氢量越大, 储氢材料对AP的催化促进作用越强. Mg2NiH4催化促进AP分解过程的作用机理为: Mg2NiH4分解释放的H2及Mg和Ni与AP分解产物发生反应.     

镁铜合金储氢材料的制备及对高氯酸铵热分解过程的影响

采用置换-扩散法制备了镁铜合金储氢材料(Mg2Cu-H), 并对其结构进行了表征. 结果表明, Mg2Cu经过氢化得到的镁铜合金储氢材料不是单一晶相, 而是MgCu2和MgH2的混合物. 用热分析法(DSC)研究了镁铜合金储氢材料对固体火箭推进剂常用氧化剂——高氯酸铵(AP)热分解过程的影响. 结果表明, 镁铜合金储氢材料可以显著促进AP的热分解过程, 加快热分解速率, 降低高温热分解温度, 使DSC表观分解热明显增大. Mg2Cu-H对AP热分解过程的促进作用明显强于Mg2Cu. 随着加入量增加, 镁铜合金储氢材料对AP热分解的催化促进作用增强. 探讨了镁铜合金储氢材料促进AP热分解过程的作用机制.     

纳米NdCoO3催化高氯酸铵热分解的DSC/TG-MS研究

采用微乳液法制备了立方晶系的NdCoO3纳米晶.利用DSC/TG-MS研究了NdCoO3对AP热分解的催化作用.结果表明,在NdCoO3的催化作用下,AP的热分解反应峰值温度下降了113℃,表观分解反应热从655 J·g-1增加到1 363 J·g-1,分解的气相产物主要有NH3,H2O,O2,HCl,N2O,NO,NO2和Cl2.在金属氧化物表面吸附生成超氧化离子(O2-)和氧离子(O-,O2-),这是加速AP分解反应的主要原因.加入NdCoO3催化AP热分解,由于对氨的氧化深度不同而导致分解放热量的增加.     

热重-差示扫描量热法研究金属铝盐与载体的相互作用

通过浸渍法将相同负载量的不同类型的金属铝盐负载在介孔分子筛HMS内外表面,用热重-差示扫描量热(TG-DSC)法研究了金属铝盐热性质的变化。将负载型金属铝盐干燥、焙烧,得到负载型催化剂Al2O3/HMS样品,用X射线衍射(XRD)、N2吸附-脱附等手段对样品进行了介孔结构表征,并初步考察了催化剂上烷基化反应的活性。实验结果表明:负载金属盐的起始分解温度均高于金属盐,证明了金属盐与载体之间有相互作用。Al2O3/HMS催化剂在对苯二酚烷基化反应中表现出不同的催化活性。这种催化活性的高低与催化剂比表面积、孔容的大小没有相应的顺变关系,与负载金属盐与载体的相互作用有关,相互作用越弱,催化剂在烷基化反应中表现出的催化活性越高。     

直形碳纳米管、分叉碳纳米管负载纳米NiO及其对高氯酸铵热分解的影响

采用射流进样催化裂解法制备了直形碳纳米管(CNTs)、分叉碳纳米管, 分别以二者为载体, 用化学沉积法制备了负载纳米NiO的复合粒子, 并研究了纳米NiO和CNTs的单一纳米粒子、简单混合物、复合物对高氯酸铵(AP)热分解的催化性能, 对催化效果的差异作了初步探讨. 结果表明: NiO/直形CNTs和NiO/分叉CNTs复合粒子比表面积大, 表面负载层的纳米NiO结晶好、粒子均匀、粒径小、分散性好. 复合粒子对AP热分解的催化效果比单一纳米粒子和简单混合物好, 其中NiO/分叉CNTs复合粒子催化效果最好, 使AP高温分解峰温降低了94.6 ℃, 使表观分解热增加了819 J/g. CNTs的载体支撑作用, 可防止NiO纳米粒子的团聚, 增大比表面积, 增加反应活性中心, 增加催化效果, 载体分叉CNTs的枝杈形结构, 有利于纳米NiO/分叉CNTs复合粒子催化性能的提高.     

纳米Co-B非晶态合金对高氯酸铵分解的催化性能

 利用化学还原法制备了纳米 Co-B 非晶态合金,并用透射电镜、X射线衍射、差示扫描量热和N2吸附表面积测试等技术对样品进行了表征. 运用差热分析研究了纳米 Co-B 非晶态合金对高氯酸铵(AP)分解的催化性能. 结果表明,加入 Co-B 非晶态合金后AP的高低温放热峰相连,合并成一个高而大的放热峰,且峰温有很大程度的降低, 这说明纳米 Co-B 非晶态合金对AP热分解有很好的催化活性. 同时, Co-B 非晶态合金能使AP的表观分解热显著增大.     

Synthesis and catalytic performance of ferrocene‐based compounds as burning rate catalysts

To overcome migration problems of ferrocene‐based burning rate catalysts and to enhance burning rate of ammonium perchlorate (AP)‐based propellants, eleven ferrocene‐based compounds ( 1 – 11 ) were synthesized by the condensation reaction of ferrocenecarbonyl chloride with corresponding amines and alcohols. The synthesis of 1 – 11 was confirmed using ¹H NMR, Fourier transform infrared and UV–visible spectroscopy. Their electrochemical properties were analyzed using cyclic voltammetry. The compounds showed redox behavior due to the presence of ferrocene. Their catalytic behavior in the thermal decomposition of AP was investigated using thermogravimetry (TG) and differential TG (DTG). In the presence of 5 wt% 1 – 11 , the thermal decomposition temperature of AP was significantly decreased. TG and DTG analyses showed that 1 – 11 had a good catalytic effect in the thermal decomposition of AP. Anti‐migration studies showed that migration of 1 – 11 was slower than that of 2,2‐bis(ethylferrocenyl)propane (catocene) and ferrocene. The effect of the presence of polar elements like oxygen and nitrogen on anti‐migration behavior of small ferrocene‐based compounds was also investigated. Oxygen‐containing compounds showed better anti‐migration behavior than nitrogen‐containing compounds.     

Multi-walled carbon nanotubes (MWCNTs)-bridged architecture of ternary Bi2O3/MWCNTs/Cu microstructure composite with high catalytic performance via two-step self-assembly

Binary and ternary microstructure composites based on CNTs have potential applications in many technological fields. In our works, we realized MWCNTs-bridged architecture of ternary Bi₂O₃/MWCNTs/Cu microstructure composite by two-step self-assembly. In order to verify its workability, we investigated catalytic performances of a series of additives for ammonium perchlorate (AP) thermal decomposition. The results showed that catalytic performance of Bi₂O₃/MWCNTs/Cu composite was better than those of the other additives, and the peak temperature for high-temperature AP decomposition reduced 151.6 °C; while no low-temperature AP decomposition was observed. MWCNTs have two crucial roles in catalytic enhancement on AP thermal decomposition: firstly, being to act as a supporter which can effectively disperse copper and Bi₂O₃ particles; secondly, being to act as a bridge, excited electrons from semiconductor can conduct and store on the surfaces of MWCNTs, which is beneficial for AP thermal decomposition. Therefore, MWCNTs-bridged architecture can synergistically enhance catalytic effect of copper and Bi₂O₃.     

Differential thermal analysis and thermogravimetry of ammonium perchlorate at pressures up to 51 ATM

The thermal decomposition of pure ammonium perchlorate (AP)was investigated in various gaseous atmospheres at pressures up to 51 atm, using a technique of thermal analysis. It is concluded that the first and second stage decompositions of AP in an atmosphere of oxygen or nitrogen are appreciably accelerated as the pressure is increased. Platinum has a catalytic effect in the high-temperature decomposition and suppresses the sublimation of AP at high temperature ranges in helium atmosphere even at 1 atm. The reaction heat for the high-temperature decomposition of AP in the platinum cell was calculated from the peak temperatures of DTA curves at various pressures to be 77.9 kcal mol^?1. The activation energies of the sublimation in helium at 1 atm and of the high-temperature decomposition in the platinum cell at various pressures of helium have also been obtained, giving similar values of 23–25 kcal mol^?1.     

Y2O3/纳米碳管复合粒子的结构及其对高氯酸铵热分解性能的研究

采用溶胶-凝胶法制备了Y₂O₃/纳米碳管复合粒子, 并用SEM, XPS, FT-IR和XRD对Y₂O₃/纳米碳管复合粒子的形貌和微观结构进行了表征. 结果表明, 纳米碳管有效承载了Y₂O₃, Y₂O₃连续均匀地负载在纳米碳管的表面, 负载量为19.53%. FT-IR 和XPS证明了Y₂O₃粒子和纳米碳管表面之间发生了化学键合. 用三种方法将相同比例的Y₂O₃/纳米碳管复合粒子与高氯酸胺(AP)进行混合, 采用差热分析(DTA)研究了三种混合样品中Y₂O₃/纳米碳管复合粒子对高氯酸铵热分解的催化性能. 结果表明, 三种混合样品中的Y₂O₃/纳米碳管复合粒子都能催化高氯酸铵的热分解, 其中通过水溶剂混合的样品中Y₂O₃/纳米碳管复合粒子的催化效果优于另外两种. 与纯高氯酸铵相比, 其样品中高氯酸铵的高温分解峰温降低了168.5 ℃, 表观分解热由371 J•g^－1提高到1410 J•g^－1. 并用不同样品中高氯酸铵热分解动力学参数对所得结果进行了理论分析.     

Preparation of NdCrO3 nanoparticles and their catalytic activity in the thermal decomposition of ammonium perchlorate by DSC/TG-MS

Orthorhombic structural perovskite NdCrO₃ nanocrystals with size of 60 nm were prepared by microemulsion method, and characterized by XRD, TEM, HRTEM, SEM, EDS and BET. The catalytic effect of the NdCrO₃ for thermal decomposition of ammonium perchlorate (AP) was investigated by DSC and TG-MS. The results revealed that the NdCrO₃ nanoparticles had effective catalysis on the thermal decomposition of AP. Adding 2% of NdCrO₃ nanoparticles to AP decreased the temperature of thermal decomposition by 87° and increased the heat of decomposition from 590 to 1073 J g⁻¹. Gaseous products of thermal decomposition of AP were NH₃, H₂O, O₂, HCl, N₂O, NO, NO₂ and Cl₂. The mechanism of catalytic action was based on the presence of superoxide ion O₂ ⁻ on the surface of NdCrO₃, and the difference of thermal decomposition of AP with 2% of NdCrO₃ and pure AP was mainly caused by the different extent of oxidation of ammonium.     

Nature of catalytic activities of CoO nanocrystals in thermal decomposition of ammonium perchlorate

This work addresses the chemical nature of the catalytic activity of X-ray "pure" CoO nanocrystals. All samples were prepared by a solvothermal reaction route. X-ray diffraction indicates the formation of CoO in a cubic rock-salt structure, while infrared spectra and magnetic measurements demonstrate the coexistence of CoO and Co 3O 4. Therefore, X-ray "pure" CoO nanocrystals are a unique composite structure with a CoO core surrounded by an extremely thin Co 3O 4 surface layer, which is likely a consequence of the surface passivation of CoO nanocrystals from the air oxidation at room temperature. The CoO core shows a particle size of 22 or 280 nm, depending on the types of the precursors used. This composite nanostructure was initiated as a catalytic additive to promote the thermal decomposition of ammonium perchlorate (AP). Our preliminary investigations indicate that the maximum decomposition temperature of AP is significantly reduced in the presence of CoO/Co 3O 4 composite nanocrystals and that the maximum decomposition peak shifts toward lower temperatures as the loading amount of the composite nanocrystals increases. These findings are different from the literature reports when using many nanoscale oxide additives. Finally, the decomposition heat for the low-temperature decomposition stages of AP was calculated and correlated to the chemical nature of the CoO/Co 3O 4 composite nanostructures.     

Pure CuCr2O4 nanoparticles: Synthesis,characterization and their morphological and size effects on the catalytic thermal decomposition of ammonium perchlorate

In the present paper a pure phase of the copper chromite spinel nanoparticles (CuCr₂O₄ SNPs) were synthesized via the sol–gel route using citric acid as a complexing agent. Then, the CuCr₂O₄ SNPs has been characterized by field emission scanning electron microscope (FE-SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD). In the next step, with the addition of Cu–Cr–O nanoparticles (NPs), the effects of different parameters such as Cu–Cr–O particle size and the Cu/Cr molar ratios on the thermal behavior of Cu–Cr–O NPs + AP (ammonium perchlorate) mixtures were investigated. As such, the catalytic effect of the Cu–Cr–O NPs for thermal decomposition of AP was evaluated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). TGA/DSC results showed that the samples with different morphologies exhibited different catalytic activity in different stages of thermal decomposition of AP. Also, in the presence of Cu–Cr–O nanocatalysts, all of the exothermic peaks of AP shifted to a lower temperature, indicating the thermal decomposition of AP was enhanced. Moreover, the heat released (ΔH) in the presence of Cu–Cr–O nanocatalysts was increased to 1490 J g⁻¹.     

多孔纳米CoFe2O4的制备及其对高氯酸铵的热分解催化性能

采用胶晶模板法制备出具有三维多孔结构的纳米CoFe₂O₄。利用X射线衍射仪(XRD)、傅里叶变换红外(FT-IR)光谱仪、扫描电镜(SEM)、透射电镜(TEM)和N₂吸附-脱附对样品的晶型和形貌结构等进行表征,采用差示扫描量热法(DSC)对比研究多孔纳米CoFe₂O₄和球形纳米CoFe₂O₄对高氯酸铵(AP)的热分解性能的影响,并考察这两种催化剂对AP催化热分解的动力学参数。结果显示,制备出的多孔纳米CoFe₂O₄样品具有典型的尖晶石结构,孔径约200 nm;比表面积明显高于40 nm球形CoFe₂O₄,达到55.646 m²·g^-1。DSC测试结果表明：多孔纳米CoFe₂O₄的加入促进了AP的热分解,最高使AP的高温分解峰温降低91.46℃,能量释放最高达1120.88 J·g^-1,是纯AP分解放热量的2.3倍;多孔纳米CoFe₂O₄具有较高的比表面积,能提高催化反应的接触面积,使AP的高温分解峰温度更低,反应活化能较小,从而表现出比球形纳米CoFe₂O₄更高的催化活性。此外,对多孔纳米CoFe₂O₄催化AP的热分解机理进行初步探索,纳米多孔催化剂对气态中间产物的作用促进了AP的热分解。     

Preparation of nano-cerium dioxide and its effect on the thermal decomposition of ammonium perchlorate

Detonation synthesis method was introduced to prepare nano-cerium dioxide. Nano-cerium oxide was obtained by this novel method and its effect on the thermal decomposition of ammonium perchlorate (AP) was studied. X-ray diffraction and transmission electron microscope were used to characterize as-prepared materials. Results showed that as-prepared cerium dioxide was cubic phase and its morphology was nearly spherical. The mean size of as-prepared cerium dioxide particles was 55 nm. Differential scanning calorimetry (DSC) was used to test the effect of as-prepared nano-cerium dioxide on the thermal decomposition of AP. Kissinger method was introduced to calculate activation energy of different specimens according to DSC data. Results indicated that nano-cerium dioxide synthesized by detonation method had catalytic effect on thermal decomposition of AP and could decrease activation energy of AP/CeO₂ mixture.     

Thermal decomposition of ammonium perchlorate based mixture with fullerenes

The effects of fullerenes, including fellerene soot (FS), extracted fullerene soot (EFS) and pure C₆₀ on the thermal decomposition of ammonium perchlorate (AP) compared with traditional carbon black (CB) catalyst has been studied by employing thermogravimetry (TG), differential thermal analysis (DTA), infrared spectroscopy (IR) and ignition temperature experiments. The results showed that the addition of CB and FS to AP reduced the activation energy as well as the temperature at maximum decomposition rate, but that of EFS and pure C₆₀ had little effect on the thermal decomposition of AP, and among all catalysts, FS was the best one.     

Preparation of Ni/TiO2 Nanoparticles and Their Catalytic Performance on the Thermal Decomposition of Ammonium Perchlorate

Metal/oxide nanoparticles are attractive because of their special structure and better properties. The Ni/TiO₂ nanoparticles were prepared by a liquid phase chemical reduction method in this paper. The obtained‐products were characterized by inductively coupled plasma (ICP), X‐ray diffraction (XRD), high‐resolution transmission electron microscopy (HRTEM) and scanning electron microscopy (SEM). The results show that Ni particles in Ni/TiO₂ nanoparticles exhibit better dispersion and the size of most Ni particles is 10 nm or so. The catalytic activity of Ni/TiO₂ nanoparticles on the thermal decomposition of ammonium perchlorate (AP) was investigated by simultaneous thermogravimetry and differential thermal analysis (TG‐DTA). Results show that composite process of Ni and TiO₂ can improve the catalytic activity of Ni nanoparticles on the thermal decomposition of AP, which is mainly attributed to the improvement of Ni dispersion in Ni/TiO₂ nanoparticles. The catalytic activity of Ni/TiO₂ nanoparticles increases with increasing the weight ratio of Ni to AP.