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.     

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.     

Cooperative effect of Fe and Ti species over Fe–Ti–Ox catalysts on the catalytic hydrolysis performance of hydrogen cyanide

FeO_x, TiO₂, and Fe–Ti–O_x catalysts were synthesized and used in the catalytic hydrolysis of hydrogen cyanide (HCN). Nearly 100% HCN conversion was achieved at 250 °C over the Fe–Ti–O_x catalyst. TiO₂ rutile was detected over TiO₂, but not over Fe–Ti–O_x, which suggested that the interaction between Fe and Ti species could inhibit the TiO₂ phase transition. Furthermore, the interaction between Fe and Ti species over Fe–Ti–O_x could promote the selectivity of NH₃ and CO. The mechanism of hydrolysis of HCN over FeO_x, TiO₂, and Fe–Ti–O_x can be given as follows: HCN + H₂O → methanamide → ammonium formate → formic acid → H₂O + CO.     

Effectively promoted catalytic activity by adjusting calcination temperature of Ce-Fe-Ox catalyst for NH3-SCR

A series of Ce-Fe-O_x catalysts prepared by the different calcination temperatures (marked as CF-X, where X represented calcination temperature) were used to the selectivity catalytic reduction of NO_x by NH₃. The results explained the relationship between calcination temperature and the sulfate species over Ce-Fe-O_x, and then investigated the surface acidity and catalytic performance. The large amounts of sulfate species were formed over CF-450 and CF-550 while it was decomposed with further the increasing of calcination temperature, which resulted in the loss of surface acidity, causing a decrease in the catalytic activity over Ce-Fe-O_x. Thereby, the CF-450 catalyst showed the best catalytic activity and over 90% NO_x conversion was obtained at 244–450 °C. Besides, the favored pore structure, more Fe³⁺ active species, higher Ce³⁺ concentration and the abundance of chemical adsorbed oxygen species, as well as the surface acid sites, would together contribute to the excellent catalytic activity of CF-450 catalyst.     

Efficient catalytic degradation of single and binary azo dyes by a novel triple nanocomposite of Mn3O4/Ag/SiO2

The strategy of structurally integrating noble metal and metal oxides is expected to offer exceptional opportunities toward emerging functions of all. We report the creation of an efficient hetero-structured nanocatalyst consisting of Mn₃O₄ core, SiO₂ shell impregnated with noble Ag nanoparticles. The triple nanocatalyst Mn₃O₄/Ag/SiO₂ was synthesized by using a facile three-step approach to disperse Ag nanoparticles between the surfaces of functionalized Mn₃O₄ and SiO₂. The physicochemical structural characterization was performed by XRD and FTIR. The surface morphologies were observed by SEM and TEM. The EDX measurements confirmed the composition of the composite. The nanocomposite has been used as a catalyst for the degradation of Direct blue 78 in the presence of sodium borohydride (NaBH₄). It has a drastic catalytic effect as compared to Mn₃O₄/Ag and Mn₃O₄. The rate constant of Direct blue 78 reduction followed the order: Mn₃O₄/Ag/SiO₂ (0.25166 min⁻¹) > Mn₃O₄/Ag (0.07971 min⁻¹) > Mn₃O₄ (0.00947 min⁻¹). The effects of different reaction conditions of the catalytic reaction have been determined. The catalytic activity of the as- synthesized nanocomposite was examined for the binary dyes system by incorporation of an additional dye (Sunset yellow). Its influence on the degradation rate and efficiency of Direct blue 78 was investigated. The nanocatalyst exhibited excellent catalytic activity towards the complete degradation of both the Direct blue 78 and Sunset yellow. The degradation percentage for these dyes reached 99.33 and 94.68%, respectively. The recovery and reusability of the Mn₃O₄/Ag/SiO₂ nanocomposite was studied in the reduction reaction of Direct blue 78. Five consecutive recovery reaction cycles were performed. They revealed high stability and constant efficiency of the catalyst for four cycles.     

Efficient monooleoyl glycerol synthesis employing hybrid ultrasonic-infrared-wave promoted reactor: Concurrent catalytic and noncatalytic esterification kinetics

For the first time, intensification of monooleoyl glycerol (MOG) synthesis has been investigated in an ultrasonic-infrared-wave (USIRW) promoted batch reactor. Esterification of octadecanoic acid (ODA) with glycerol (Gl) has been conducted [using Amberlyst 36 wet catalyst] in three different reactors, namely traditional batch reactor (TBR), infrared wave promoted batch reactor (IRWPBR), and USIRW-promoted batch reactor (USIRWPBR) to assess the relative efficacy. The energy-efficient USIRWPBR remarkably intensifies the ODA-Gl esterification as manifested through superior ODA conversion (92.5 ± 1.25%) compared to that achieved in IRWPBR (79.8 ± 1.2%) and TBR (36.39 ± 1.25%). The most favorable reaction condition for optimum ODA conversion and maximum MOG yield was identified through statistical optimization over a selected parametric range, namely 3-5 Gl/ODA mole ratio, 0.004-0.006 g/mL Amberlyst 36 catalyst concentration, 300-700 rpm impeller speed, and 333-353 K reaction temperature. The present study also reports the formulation and validation of an innovative reaction kinetics, that is, concurrent noncatalytic and heterogeneously catalyzed (CNCHC) reaction mechanism in addition to the conventional heterogeneous kinetic models (LH and Eley-Rideal mechanisms). Under combined USIRW, the CNCHC esterification mechanism could best describe ODA-Gl esterification (R² = 0.98) compared to LH (R² = 0.97) and Eley-Rideal (R² = 0.88) mechanisms. The optimal product (MOG) was characterized by differential scanning calorimetry and thermogravimetric analysis to assess its crystallization property and thermal stability for possible application as plasticizer/fuel additives.