(4R,5R)-1,3-二氧戊环-2,2-二苯基-4,5-二-[亚甲基-N,N'-(1-甲基-4-羟基苯甲醛)]的合成及其催化性能

以L-酒石酸和二苯甲酮为原料,经酯化、缩酮、加成、消除、还原和缩合等反应合成了一种新型席夫碱类化合物——(4R,5R)-1,3-二氧戊环-2,2-二苯基-4,5-二-[亚甲基-N,N'-(1-甲基-4-羟基苯甲醛)](4),其结构经1H NMR,13C NMR和LC-MS表征。以二烷基锌对苯甲醛的不对称加成为模板反应,考察了4的不对称催化性能。实验结果表明,4对该反应具有一定的催化效果(ee值52%)。     

铜基/氧化锆催化剂的应用及改性研究进展

ZrO2具有弱酸碱性、氧化还原性、良好的热稳定性和机械强度,在催化领域得到广泛应用。以Zr O2为载体的铜基催化剂因其活性高,选择性好,性能稳定,受到越来越多的关注。本文介绍了Cu/Zr O2催化剂在醇类的水蒸气重整制氢、CO/CO2加氢合成低碳醇、二乙醇胺脱氢、乙醇直接合成乙酸乙酯和低温水煤气变换方面的应用。综述了添加不同助剂对Cu/Zr O2催化剂物化及催化性能的影响。     

Nanocrystalline TiO2, via green combustion synthesis,as an efficient and reusable catalyst for the preparation of 1,8‐dioxooctahydroxanthenes and 1,8‐dioxodecahydroacridines

Nanocrystalline TiO₂ is synthesized using a green combustion method and used as a recyclable catalyst for the one‐pot multicomponent synthesis of 1,8‐dioxodecahydroacridines and 1,8‐dioxooctahydroxanthenes, under solvent‐free conditions. This method is mild, environmentally friendly, inexpensive and highly effective for obtaining good to excellent yields of the products. Copyright © 2015 John Wiley & Sons, Ltd.     

CH4/空气简化动力学机理数值验证

选择绕圆柱预混燃烧算例，验证CH₄/空气三种简化动力学机理（16s41r、15s19r和53s325r）.考虑均匀来流，忽略湍流和湍流与燃烧相互作用以及燃料扩散效应，假设层流有限反应速率，采用保自由流5阶WENO格式求解多组分Euler方程组，得到CH₄/空气预混燃烧流场温度等值线、沿驻点线压力和温度及其CH₄、CO和CO₂质量百分数分布.结果表明：三种简化动力学机理给出的流场均出现弓形激波和火焰面，弓形激波和火焰驻点距离及其形状、诱导区宽度和简化动力学机理相关.当圆柱直径增大，弓形激波和火焰向圆柱上游移动，对应的驻点距离均增大，诱导区宽度变短，点火延时变小，但火焰和弓形激波位置次序未变化.53s325r模型要比16s41r模型和15s19r模型精度要高，点火延时覆盖的压力和温度范围也较宽，所有简化机理均未完全反应，在较大圆柱直径下游达到化学平衡.     

不同晶体结构Gd2(MoO4)3:Eu3+荧光粉的合成及其发光性能研究

采用溶胶凝胶-燃烧法,柠檬酸为络合剂合成出系列Gd₂(MoO₄)₃:Eu³⁺荧光粉.利用X射线衍射(XRD)、扫描电子显微镜(SEM)和荧光光谱对样品的结构、形貌和发光性能进行了研究.XRD分析表明:稀土离子与柠檬酸为1:0.5时,800℃热处理获得单斜结构的Gd₂(MoO₄)₃:Eu³⁺荧光粉.单斜结构的Gd₂(MoO₄)₃:Eu³⁺荧光粉到正交结构的Gd₂(MoO₄)₃:Eu³⁺荧光粉的转换可以通过改变稀土离子与柠檬酸摩尔比和热处理温度等合成条件实现.Gd₂(MoO₄)₃:Eu³⁺荧光粉的形貌受合成条件的影响.荧光光谱研究表明:Gd₂(MoO₄)₃:Eu³⁺荧光粉的主发射峰位于616 nm处来自于Eu³⁺的⁵D₀→⁷F₂电偶极跃迁.正交结构的Gd₂(MoO₄)₃:Eu³⁺荧光粉发射强度明显高于单斜结构的荧光粉.计算⁵D₀→⁷F₂与⁵D₀→⁷F₁跃迁发射的相对强度比值表明:正交结构的Gd₂(MoO₄)₃:Eu³⁺中Eu³⁺局域环境的对称性较高。     

Can (H2O) n (n = 1–2) as effective catalysts in the CH2OO + H2S reaction under tropospheric conditions?

The addition reaction of CH₂OO?+?H₂S → HSCH₂OOH without and with catalyst X (X?=?H₂O and (H₂O)₂) has been investigated by CCSD(T)-F12a/VTZ-F12//B3LYP/aug-cc-pVTZ method and canonical variational transition state theory with small curvature tunneling correction. When H₂O was introduced in the CH₂OO?+?H₂S reaction, it not only acts as a catalyst for producing HSCH₂OOH, but also plays as a reactant to forming HOCH₂OOH. The formation channel of HSCH₂OOH is more important than the formation channel of HOCH₂OOH with its calculated rate constant larger by 11.0–43.2 times within the temperature 280–320?K. Then, (H₂O)₂ catalysed CH₂OO?+?H₂S → HSCH₂OOH reaction has been taken into account with its rate lower 1.9–4.2 times than the reaction of CH₂OO?+?H₂S → HSCH₂OOH with water. Also, CH₂OO?+?H₂S with H₂O cannot compete with the CH₂OO?+?H₂S reaction without water. This is different from CH₂OO?+?(H₂O)₂ reaction, which is about 4 orders of magnitude larger than the rate constant for CH₂OO?+?H₂O reaction. Such discrepancy is possible because C(CH₂OO)···O(H₂O) interaction has been enhanced more obviously by H₂O as compared to that of C(CH₂OO)···O(H₂S) interaction.     

High effects of smoke suppression and char formation of Ni?Mo/Mg(OH)2 for polypropylene

The Ni? Mo/Mg(OH)₂ (NMM) hybrid as an efficient flame retardancy and smoke suppression composite for polypropylene (PP) was synthesized through Ni? Mo co‐precipitation on the surface of Mg(OH)₂ (MH) hexagonal nanosheets. Compared to PP/MH, PP/NMM exhibited excellent smoke suppressing and flame retardancy on the heat release rate, total heat release, smoke production rate, total smoke production, CO production rate and total CO production with the same loading. The reduced hazard of PP/NMM was mainly attributed to the high physical barrier effect of compact char residues on heat, smoke and combustible gas. The mechanism study indicated that multiwalled carbon nanotubes (MWCNTs) generated from the catalytic carbonization of PP by the Ni? Mo compound could play the role of “rebar” to strengthen the char residues, avoid the generation of cracks and form highly compact char layer. Furthermore, MgO could facilitate the production of MWCNTs through changing the pyrolysis process of PP and increasing the reaction time between pyrolysis gas and Ni? Mo compound. Hence, the new Ni? Mo/MH catalyst hybrid may explore the potential for solving the tough problem of the flammability and heavy smoke of the polyolefins system.     

石英砂粒径对水合物沉积物力学性质的影响

利用自主研发的水合物沉积物原位合成与力学性质测试的高压低温三轴仪,通过多级加荷的试验方法,以不同粒径的砂粒作为沉积物骨架进行三轴压缩试验,得到了剪切过程的应力-应变关系曲线,以及不同粒径尺寸沉积物的强度,还有剪切过程中的体积变化关系。结果表明:含水合物沉积物强度随着沉积物粒径尺寸的增大而增强;在降压剪切过程中,所有粒径的水合物沉积物式样均有明显的剪缩现象。     

Dimensional scaling of flame propagation in discrete particulate clouds

The critical dimension necessary for a flame to propagate in suspensions of fuel particles in oxidiser is studied analytically and numerically. Two types of models are considered: First, a continuum model, wherein the individual particulate sources are not resolved and the heat release is assumed spatially uniform, is solved via conventional finite difference techniques. Second, a discrete source model, wherein the heat diffusion from individual sources is modelled via superposition of the Green's function of each source, is employed to examine the influence of the random, discrete nature of the media. Heat transfer to cold, isothermal walls and to a layer of inert gas surrounding the reactive medium are considered as the loss mechanisms. Both cylindrical and rectangular (slab) geometries of the reactive medium are considered, and the flame speed is measured as a function of the diameter and thickness of the domains, respectively. In the continuum model with inert gas confinement, a universal scaling of critical diameter to critical thickness near 2:1 is found. In the discrete source model, as the time scale of heat release of the sources is made small compared to the interparticle diffusion time, the geometric scaling between cylinders and slabs exhibits values greater than 2:1. The ability of the flame in the discrete regime to propagate in thinner slabs than predicted by continuum scaling is attributed to the flame being able to exploit local fluctuations in concentration across the slab to sustain propagation. As the heat release time of the sources is increased, the discrete source model reverts back to results consistent with the continuum model. Implications of these results for experiments are discussed.     

Tuning the Reactivities of the Heteronuclear [AlnV3−nO7−n]+ (n=1, 2) Cluster Oxides towards Methane by Varying the Composition of the Metal Centers

The thermal gas-phase reactions of [Al₂VO₅]⁺ and [AlV₂O₆]⁺ with methane have been explored by using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry complemented by high-level quantum chemical calculations. Both cluster ions chemisorbed methane as the major reaction channels at room temperature. [Al₂VO₅]⁺ could break only one C−H bond to liberate CH₃, whereas [AlV₂O₆]⁺ exhibited higher oxidizing ability such that it brings about the selective generation of formaldehyde. Mechanistic aspects are revealed and the crucial roles of the metal centers are discussed.