高压下β-HMX热分解机理的ReaxFF反应分子动力学模拟

采用ReaxFF反应分子动力学方法研究了不同压缩态β-HMX晶体(ρ=1.89、2.11、2.22、2.46、2.80、3.20 g·cm^-3)在T=2500 K时的热分解机理, 分析了压力对初级和次级化学反应速率的影响、高压与低压下初始分解机理的区别以及造成反应机理发生变化的原因. 发现HMX的初始分解机理与压力(或密度)相关. 低压下(ρ<2.80 g·cm^-3)以分子内反应为主, 即N－NO₂键的断裂、HONO的生成以及分子主环的断裂(C－N键的断裂). 高压下(ρ≥2.80 g·cm^-3)分子内反应被显著地抑制, 而分子间反应得到促进, 生成了较多的O₂、HO等小分子和大分子团簇. 初始分解机理随压力的变化导致不同密度下的反应速率和势能也有所不同. 本文在原子水平对高压下HMX反应机理的深入研究对于认识含能材料在极端条件下的起爆、化学反应的发展以及爆轰等具有重要意义.     

回流水热合成均分散纳米α-Fe2O3单晶粒子

系统地研究了以Fe(NO₃)₃为原料，回流水热合成均分散α-Fe₂O₃纳米粒子。实验结果显示:当pH=1时，随着水热时间的增加，由透射电镜测试可知，多孔性纺锤形α-Fe₂O₃单晶转变成粒径在45 nm左右的均分散菱形单晶;而Fe(NO₃)₃用氨水中和形成Fe(OH)₃凝胶后，随着初始pH值的增加，完全转变成α-Fe₂O₃所需的时间增加、粒径减小，但产物的结构更为完整。另外通过实验发现，反应体系中存在的电解质对α-Fe₂O₃晶体的生成有促进作用。同时对初始pH值及电解质对α-Fe₂O₃生成速率的影响机理进行了分析。     

铈钛混合氧化物负载磷钨酸吸附-分解NOx性能

通过软化学途径合成了铈钛混合氧化物(CeO₂-TiO₂)载体材料, 并分别通过等体积浸渍法和机械研磨法负载磷钨酸(H₃PW₁₂O₄₀)。采用FTIR、XRD、SEM和BET比表面积测定对CeO₂-TiO₂及负载型多酸催化剂进行了表征;考察了负载量、负载方法、吸附温度等因素对催化剂吸附NO_x效率的影响;选取吸附性能最佳的催化剂进行了NO_x催化分解实验, 探讨了NO_x吸附-分解机理。结果表明:相对于等体积浸渍法, 机械研磨法更适合此类载体负载H₃PW₁₂O₄₀, 其NO_x吸附效率均高于H₃PW₁₂O₄₀及载体本身;在0~60%的负载量范围内, 随着H₃PW₁₂O₄₀负载量的增加, 负载型催化剂吸附NO_x的效率呈上升趋势, 负载量为40%时NO_x吸附效率最佳, 达90%;吸附过程中NO_x与催化剂活性组分H₃PW₁₂O₄₀发生作用, 生成NOH⁺, H₃PW₁₂O₄₀二级结构中结晶水对催化剂吸附NO_x有重要作用;当温度从150℃升至 450℃时, 被吸附的NO_x发生分解, 分解产物的组成与N₂的收率均受升温速率的影响, 升温速率越快, N₂收率越高。向吸附分解NO_x后的催化剂床层通入含有水蒸气的空气, 可有效补充NO_x分解过程中H₃PW₁₂O₄₀失去的结晶水, 从而恢复催化剂优良的NO_x吸附分解性能, 实现催化剂的有效再生利用。     

Pt/Ce0.6Zr0.4O2催化剂催化氧化碳烟过程中活性氧对NO-NO2循环及表面含氧物种的分解作用简

通过在Ce_0.6Zr_0.4O₂载体上浸渍Pt（NO₃）₂制得Pt/Ce_0.6Zr_0.4O₂催化剂,该催化剂在松散接触条件下,于NO+O₂或O₂气氛中均表现出比Pt/Al₂O₃更好的碳烟氧化性能. 进一步研究表明,Pt/Ce_0.6Zr_0.4O₂催化剂中的Pt 与Ce_0.6Zr_0.4O₂存在相互作用,使得催化剂在一定温度范围内对活性氧的利用率大为提高,从而促进了气氛中NO↔NO₂的循环,乃至碳烟与NO₂的反应和碳烟表面含氧中间物种的生成;更重要的是,这部分活性氧本身可加速含氧中间物种的分解. 因此,在NO + O₂的气氛中,Pt/Ce_0.6Zr_0.4O₂催化剂的碳烟起燃温度比Pt/Al₂O₃降低了34 ℃.     

高硅 Na-ZSM-5 分子筛表面 NO 的常温吸附-氧化机理

 采用程序升温表面反应 (TPSR) 和原位漫反射红外光谱 (DRIFTS) 等手段研究了常温下 NO 和 O₂ 在高硅 Na-ZSM-5 分子筛上吸附-氧化反应机理. 结果表明, Na-ZSM-5 分子筛上 NO 的催化氧化过程中伴随着显著的 NO₂ 物理吸附, 表现为 NO 氧化和 NO₂ 吸附间的动态平衡. Na-ZSM-5 分子筛表面 NO_x 吸附物种的 TPSR 和原位 DRIFTS 表征表明, 化学吸附的 NO 和气相中的 O₂  在 Na-ZSM-5 表面反应生成吸附态的 NO₃, 并继续与 NO 作用生成弱吸附的 NO₂  和 N₂ O₄, 它们吸附饱和后释放出来; 其中, 强吸附的 NO₃ 在 NO 氧化过程中起到了反应中间体的作用, 同时也促进了 NO 的吸附.     

HO2自由基与NO2反应通道的理论研究

应用密度泛函理论DFT/B3LYP对HO₂＋NO₂反应进行了研究, 在B3LYP/6-311G^**和CCSD(T)/6-311G^**水平上计算了HO₂自由基与NO₂分子反应的单重态和三重态反应势能面, 计算结果表明, 单重态反应势能面中的直接氢抽提反应机理是此反应的主要反应通道, 即HO₂自由基的氢原子转移到NO₂分子的氮原子上形成产物P₁ (HNO₂＋³O₂), 另一个可能的反应通道是单重态反应势能面上HO₂中的端位氧原子进攻NO₂分子中的氮原子形成中间体1 (HOONO₂), 接着中间体1 (HOONO₂)经过氢转移形成产物P₂ (trans-HONO＋³O₂), 以上两个反应通道都是放热反应通道, 分别放热90.14和132.52 kJ•mol^－1.     

HO2自由基与NO2反应通道的理论研究

应用密度泛函理论DFT/B3LYP对HO₂＋NO₂反应进行了研究, 在B3LYP/6-311G^**和CCSD(T)/6-311G^**水平上计算了HO₂自由基与NO₂分子反应的单重态和三重态反应势能面, 计算结果表明, 单重态反应势能面中的直接氢抽提反应机理是此反应的主要反应通道, 即HO₂自由基的氢原子转移到NO₂分子的氮原子上形成产物P₁ (HNO₂＋³O₂), 另一个可能的反应通道是单重态反应势能面上HO₂中的端位氧原子进攻NO₂分子中的氮原子形成中间体1 (HOONO₂), 接着中间体1 (HOONO₂)经过氢转移形成产物P₂ (trans-HONO＋³O₂), 以上两个反应通道都是放热反应通道, 分别放热90.14和132.52 kJ•mol^－1.     

Ni基催化剂催化燃油重整耦合选择性催化还原NOx反应

分别以La₂O₂CO₃, CeO₂, ZrO₂和Al₂O₃为载体, 采用浸渍法制备了Ni基重整催化剂, 并以正十二烷模拟车载燃油进行催化重整反应以同时制备小分子碳氢化合物(HCs)和H₂, 考察了其在4wt%Ag/Al₂O₃上选择性催化还原(HC-SCR)氮氧化物(NO_x)的性能. 采用N₂吸附-脱附、X射线粉末衍射、H₂程序升温还原和热重等手段对Ni基催化剂进行了表征. 结果表明, 随着重整催化剂氧化还原性能增强, 产物中H₂浓度增加, 可参与SCR反应的HCs含量减少, 从而导致重整-SCR耦合体系上NO_x净化活性温度窗口向低温移动, NO_x最高转化率降低. Ni/ZrO₂+Ag/Al₂O₃耦合体系中H₂/HCs符合SCR反应所需的最优比例, 在柴油车典型排气温度范围内表现出良好的NO_x净化能力. 同时, 在Ni/ZrO₂+Ag/Al₂O₃耦合体系上考察了其燃油重整-SCR的活性稳定性. 结果显示, 重整催化剂的耐久性有待进一步提高.     

基于 H2/O2 等离子体和钛硅沸石的丙烯气相环氧化方法

 将 H₂/O₂ 非平衡等离子体现场产生的气态 H₂O₂和丙烯与耦合反应器中钛硅沸石 TS-1 直接接触, 实现了丙烯气相环氧化反应. 结果表明, 非平衡等离子体生成气态 H₂O₂ 的速率由介质阻挡放电的输入功率决定, 环氧丙烷的生成速率和选择性取决于钛硅沸石催化剂和反应条件. 在 H₂ 和 O₂ 进料流量分别为 170 和 8 ml/min, 介质阻挡放电输入功率为 3.5 W, 环氧化反应温度为 110 ^oC, 丙烯进料量为 18 ml/min, 催化剂用量为 0.8 g 的条件下, 生成环氧丙烷产率达 246.9 g/(kg•h)、环氧丙烷选择性和 H₂O₂ 有效利用率分别为 95.4% 和 36.1%, 反应 36 h 内未见催化剂失活.     

等离子体在同时去除NOx和碳烟催化反应中的作用

采用程序升温反应(TPR)技术,研究了等离子体辅助同时催化去除富氧柴油机尾气中NO_x和碳烟(soot)的反应特性.研究结果表明,等离子体提高了同时去除NO_x-soot的催化反应活性,降低了碳烟的燃烧温度,使碳烟起燃温度从300 ℃降到280 ℃,燃尽温度从425 ℃降到380 ℃;同时,等离子体辅助提高了NO_x转化为N₂的效率,使催化选择性从1.12％提高到1.53％.本文还分别研究了在NO和O₂的环境中,有或没有等离子体作用下,碳烟在催化作用下的去除特性.等离子体作用使得NO在和O₂共存、只有NO和只有O₂存在的各种条件下,碳烟的催化燃烧活性都有不同程度的提高,促进了N₂的生成.此外,本文也对等离子体辅助同时催化去除NO_x-soot的机理进行了探讨.     

The effect of crystal structure on the thermal reactivity of CL-20 and its C4-bonded explosives

The critical temperature and mechanism functions for thermal decomposition of ε-CL-20, RS-ε-CL-20, α-CL-20, ε-CL-20/C4, and RS-ε-CL-20/C4 were evaluated based on non-isothermal TG data. A two-step mechanism has been found for thermal decomposition of α-CL-20, ε-CL-20/C4, and RS-ε-CL-20/C4, where the initial step is partly controlled by crystal structure of CL-20. The more reasonable mean activation energies could be obtained after peak separation for each individual steps. In fact, the activation energy for the post integrated process is almost equivalent with that of the second step, indicating that the total activation energy at the main decomposition process is dominated by thermolysis of CL-20 molecular. Besides, it has been found that the decomposition of C4 matrix does not affect the decomposition of normal ε-CL-20, resulting in identical activation energy and reaction model. However, the interaction between the C4 matrix and RS-ε-CL-20 is significant especially at the initial stage, where the activation energy of RS-ε-CL-20/C4 was overestimated before peak separation, while the activation energy for the second step due to thermolysis of CL-20 molecular is underestimated. The first decomposition step for α-CL-20, ε-CL-20/C4, and RS-ε-CL-20/C4 could be considered as autocatalytic process (AC model), whereas the second as JMA model, which is also applicable to that of pure ε-CL-20 and RS-ε-CL-20. Moreover, The critical temperatures of thermal explosion (T _b) are obtained as 205.6, 205.5, 209.4, 214.4, and 227.5 °C for α-CL-20, ε-CL-20, RS-ε-CL-20, ε-CL-20/C4, and RS-ε-CL-20/C4, respectively. It proves that the C4 matrix could stabilize ε-CL-20 while the crystal form of CL-20 has little effect on its thermal stability.     

Investigation on the thermal behaviour of Mg(NO3)2·6H2O I. The decomposition behaviour

The decomposition mechanism of Mg(NO₃)₂·6H₂O was studied by means of simultaneous TG, DTG and DTA method combined with EGA technique under conventional and quasi isothermal-quasi isobaric conditions. It has been found that Mg(NO₃)₂·6H₂O melts at 89 °C in a congruent way. The solution formed begins to boil at 147 °C. The water loss process of the salt hydrate and the decomposition process of the Mg(NO₃)₂ always overlap to some extent. Accordingly, Mg(NO₃)₂ of stoichiometric composition cannot be prepared thermally, because the compound always contains some basic salt. The last part of water departs in the vicinity of 270 °C with extreme rapidity. In contrast to expectations the compound decomposes in pure “self-generated” atmosphere at a temperature lower by about 80 °C than in the presence of air which contains a small amount of the gaseous decomposition product.     

Ordering and Clathrate Hydrate Formation in Co‐deposits of Xenon and Water at Low Temperatures

Local ordering in co‐deposits of water and xenon atoms produced at low temperatures can be followed uniquely by ¹²⁹Xe NMR spectroscopy. In water‐rich samples deposited at 10 K and observed at 77 K, xenon NMR results show that there is a wide distribution of arrangements of water molecules around xenon atoms. This starts to order into the definite coordination for the structure I, large and small cages, when samples are annealed at ～140 K, although the process is not complete until a temperature of 180 K is reached, as shown by powder Xray diffraction. There is evidence that Xe ? 20 H₂O clusters are prominent in the early stages of crystallization. In xenon‐rich deposits at 77 K there is evidence of xenon atoms trapped in Xe ? 20 H₂O clusters, which are similar to the small hydration shells or cages observed in hydrate structures, but not in the larger water clusters consisting of 24 or 28 water molecules. These observations are in agreement with results obtained on the formation of Xe hydrate on the surface of ice surfaces by using hyperpolarized Xe NMR spectroscopy. The results indicate that for the various different modes of hydrate formation, both from Xe reacting with amorphous water and with crystalline ice surfaces, versions of the small cage are important structures in the early stages of crystallization.     

Thermal decomposition of gallium nitrate hydrate Ga(NO<Subscript>3</Subscript>)<Subscript>3</Subscript>×<Emphasis Type="Italic">x</Emphasis>H<Subscript>2</Subscript>O

The thermal decomposition of gallium nitrate hydrate (Ga(NO₃)₃·xH₂O) to gallium oxide has been studied by TG/DTG and DSC measurements performed at different heating rates. It is concluded that 8 water molecules are present in the hydrate compound. The anhydrous gallium nitrate does not form at any temperature as the reaction consists of coupled dehydration/decomposition processes that occur with a mechanism dependent on heating rate. TG measurements performed with isothermal steps (between 31 and 115°C) indicate that Ga(OH)₂NO₃ forms in the first stage of the reaction. Such a compound undergoes further decomposition to Ga(OH)₃ and Ga(NO₃)O, compounds that then decompose respectively to Ga(OH)O and finally to Ga₂O₃ and directly to Ga₂O₃. Diffuse reflectance Fourier transform IR spectroscopy (DRIFTIR) has been of help in assessing that the reaction consists of parallel dehydration/decomposition processes.     

Intermolecular interactions,vibrational spectra,and detonation performance of CL-20/TNT cocrystal

We report the structural properties, intermolecular interactions (Hirshfeld surface analysis and reduced density gradient [RDG] analysis), radial distribution function analysis, vibrational frequencies, and detonation performance for the pure ε-CL-20, TNT, and ε-CL-20/TNT cocrystal to understand how noncovalent interactions affect the impact sensitivity of the cocrystals. The results indicate that the simulated lattice parameters and densities of all the three crystals were consistent with the experiments. Major driving forces for the formation of the ε-CL-20/TNT cocrystal are O H and N O interactions, but the O O interactions may serve as a crucial stabilizing force. The calculated Raman spectra of the CL-20/TNT cocrystal and the experimental result have the same trend. The Roman peaks of the cocrystal in the range 1,200–1,750 cm⁻¹ may result from the coupling of the ε-CL-20 and TNT molecules. Similar crystal packing for TNT and CL-20 leads to the high density for the cocrystal. The cocrystal displays low impact sensitivity because of the p–π interactions. Our work may offer useful information for cocrystallization technology and its practical applications in the field of energetic materials.     

Molecular Dynamics Simulation of Methane Hydrate Decomposition in the Presence of Alcohol Additives

The decomposition process of methane hydrate in pure water and methanol aqueous solution was studied by molecular dynamics simulation. The effects of temperature and pressure on hydrate structure and decomposition rate are discussed. The results show that decreasing pressure and increasing temperature can significantly enhance the decomposition rate of hydrate. After adding a small amount of methanol molecules, bubbles with a diameter of about 2 nm are formed, and the methanol molecules are mainly distributed at the gas-liquid interface, which greatly accelerates the decomposition rate and gas-liquid separation efficiency. The radial distribution function and sequence parameter analysis show that the water molecules of the undecomposed hydrate with ordered ice-like configuration at a temperature of 275 K evolve gradually into a long-range disordered liquid structure in the dynamic relaxation process. It was found that at temperatures above 280 K and pressures between 10 atm and 100 atm, the pressure has no significant effect on hydrate decomposition rate, but when the pressure is reduced to 1 atm, the decomposition rate increases sharply. These findings provided a theoretical insight for the industrial exploitation of hydrates.     

Thermal decomposition of cobalt nitrato compounds: Preparation of anhydrous cobalt(II)nitrate and its characterisation by Infrared and Raman spectra

The thermal decomposition of Co(NO₃)₂·6H₂O (1) as well as that one of NO[Co(NO₃)₃] (Co(NO₃)₂·N₂O₄) (2) was followed by thermogravimetric (TG) measurements, X-ray recording and Raman and IR spectra. The stepwise decomposition reactions of 1 and 2 leading to anhydrous cobalt(II)nitrate (3) were established. In N₂ atmosphere, cobalt oxides are finally formed whereas in H₂/N₂ (10% H₂) cobalt metal is produced. Rapid heating of cobalt(II)nitrate hexahydrate causes melting (formation of a hydrate melt) and therefore side reactions in the hydrate melt by incoupled reactions and evolution/evaporation of different species as, e.g., HNO₃, NO₂, etc. In case of larger amounts in dense packing in the sample container, the formation of oxo(hydoxo)nitrates is possible at higher temperature. For 2, its thermal decomposition to 3 was followed and its decomposition mechanism is proposed.     

Spectral characteristics of water clusters in the presence of nitrogen dioxide

The absorption of NO₂ molecules by a water cluster containing 25 molecules was studied by molecular dynamics. The calculated dielectric characteristics of a system of (NO₂) _i (H₂O)₂₅ clusters (1 ≤ i ≤ 6) were compared with similar data for a cluster system of pure water. The ability of the disperse water system that trapped NO₂ molecules to absorb IR radiation increased, and the rate of the absorbed energy emission decreased. The Raman spectrum of the disperse system that absorbed NO₂ molecules changed most significantly in the low-frequency range. The emission time of cluster-generated radiation was much smaller than the lifetime of the clusters.     

The effect of crystal structure on the thermal reactivity of CL-20 and its C4 bonded explosives (I): thermodynamic properties and decomposition kinetics

The crystal structure, thermal behavior, and decomposition kinetics of ε-CL-20, RS-ε-CL-20, α-CL-20, ε-CL-20/C4, and RS-ε-CL-20/C4 were investigated by nonisothermal FTIR, TG, and DSC techniques. It was found that the thermal decomposition of α-CL-20, ε-CL-20/C4, and RS-ε-CL-20/C4 could be considered as a two-step process and the initial step is partly controlled by crystal structure. However, the crystal structure could only affect the initial step of decomposition and the total heat release, and the heat release of RS-ε-CL-20 is the highest compared with α- and normal ε-CL-20. In addition, the activation energy of studied materials was calculated by Kissinger method and modified KAS method, which was compared with the results obtained by other researchers. It was indicated that the obtained activation energy of ε-CL-20 by Kissinger method is about 176.0 kJ mol^?1, which is almost the same with the results from the literatures by STABIL and Noniso-TG methods. It was noticed that the crystal structure has significant effect on the initial activation energy distribution of CL-20, while in case of second stage (α = 0.30–0.85) this effect is relatively small, resulting in identical decomposition mechanism. Moreover, the kinetic compensation effects show that the studied materials could be divided into two groups, one including ε-CL-20, RS-ε-CL-20, α-CL-20, and ε-CL-20/C4 which decompose at solid state and another including ε-CL-20/Formex and RS-ε-CL-20/C4 which decompose at partial liquid state, resulting in different kinetic compensation effects. It reveals that the C4 base could affect the distribution of activation energy of ε-CL-20 and RS-ε-CL-20 in a totally different way.