炭石墨材料制备热反应机理、影响因素的浅析

从有机物分子结构、热稳定性,有机物热反应机理角度看炭石墨材料生产中炭化与温度关系及影响炭石墨材料性能的一些因素。

ReaxFF MD方法揭示的JP-10热解吸热与氧化放热机理

认识裂解吸热和氧化放热反应机理对发展高超声速飞行器所需要的吸热型碳氢燃料极为重要。通过基于ReaxFF力场的反应分子动力学模拟(ReaxFF MD),揭示了JP-10热裂解吸热与氧化放热的微观反应机理。升温模拟结果表明,JP-10氧化体系总反应热效应由吸热转变为放热的转折点在2600 K附近,吸热阶段开环反应的吸热量约占总吸热量的64%。在JP-10氧化阶段,H自由基和O_(2)反应生成HO_(2),进而生成HO自由基以及含氧自由基生成H_(2)O的反应会大量释热,约占总放热量的54%。结果表明:基于ReaxFF MD模拟、通过反应热分析识别重要反应是一种有潜力认识燃料分子结构对燃料裂解吸热能力及裂解产物组成对燃料氧化释热能力影响规律的新途径。

Mechanism for thermite reactions of aluminum/iron-oxide nanocomposites based on residue analysis

Sol-gel method was employed to combine Al and iron-oxide to form nanocomposites （nano-Al/xero-Fe2O3 and micro-Al/xero-Fe2O3）. SEM, EDS and XRD analyses were used to characterize the nanocomposites and the results indicated that nano-Al and micro-Al were compactly wrapped by amorphous iron-oxide nanoparticles （about 20 nm）, respectively. The iron-oxide showed the mass ratio of Fe to O as similar as that in Fe2O3. Thermal analyses were performed on two nanocomposites, and four simple mixtures （nano-Al＋xero-Fe2O3, nano-Al＋micro-Fe2O3, micro-Al＋xero-Fe2O3, and micro-Al＋micro-Fe2O3） were also analyzed. There were not apparent distinctions in the reactions of thermites fueled by nano-Al. For thermites fueled by micro-Al, the DSC peak temperatures of micro-Al/Xero-Fe2O3 were advanced by 68.1 ℃ and 76.8 ℃ compared with micro-Al＋xero-Fe2O3 and micro-Al＋micro-Fe2O3, respectively. Four thermites, namely, nano-Al/xero-Fe2O3, nano-Al＋micro-Fe2O3, micro-Al/xero-Fe2O3, and micro-Al＋micro-Fe2O3, were heated from ambient temperature to 1020 ℃, during which the products at 660 ℃ and 1020 ℃ were collected and analyzed by XRD. Crystals of Fe, FeAl2O4, Fe3O4,α-Fe2O3, Al,γ-Fe2O3, Al2.667O4, FeO andα-Al2O3 were indexed in XRD patterns. For each thermite, according to the specific products, the possible equations were given. Based on the principle of the minimum free energy, the most reasonable equations were inferred from the possible reactions.

Reaction mechanisms of low-grade molybdenum concentrate during calcification roasting process

The effects of Ca-based additives on roasting properties of low-grade molybdenum concentrate were studied. The resultsshow that calcium-based additives can react with molybdenum concentrate to form CaSO4 and CaMoO4. The initial oxidationtemperature of MoS2 is 450℃, while the formation of CaMoO4 and CaSO4 occurs above 500℃. The whole calcification reactionsare nearly completed between 600 and 650℃. However, raising the temperature further helps for the formation of CaMoO4 but isdisadvantageous to sulfur fixing rate and molybdenum retention rate. Calcification efficiency of Ca-based additives follows theorder： Ca（OH）2〉CaO〉CaCO3. With increasing the dosage of Ca（OH）2, the molybdenum retention rate and sulfur-fixing rate rise, butexcessive dosages would consume more acid during leaching process. The appropriate mass ratio of Ca（OH）2 to molybdenumconcentrate is 1：1. When roasted at 650 ℃ for 90 min, the molybdenum retention rate and the sulfur-fixing rate of low-grademolybdenum concentrate reach 100% and 92.92%, respectively, and the dissolution rate of molybdenum achieves 99.12% withcalcines being leached by sulphuric acid.

Pyrolysis of CL20-BTF Co-crystal via ReaxFF-lg Reactive Force Field Molecular Dynamics Simulations

To obtain detailed information on the potential energy, the evolution of species, the initial reaction paths, and thermal decomposition products, we conducted simulations on pyrolysis process of CL20/BTF co-crystal using the ReaxFF/lg reaction force field, with temperature set at 2000 K to 3000 K. With the analysis of evolution curves of potential energy based on exponential function, we obtain the overall characteristic time. Via a description of the total package reaction with classical Arrhenius law, we obtain the activation energy of CL20/BTF co-crystal： Ea=60.8 kcal/mol. Based on the initial path of CL20/BTF co-crystal thermal decomposition we studied, we conclude that N-NO2 bond of CL20 molecules breaks first, working as a dominant role in the initial stage of thermal decomposition under the condition of different temperatures, and that all CL20 molecules completely decompose before BTF molecular regardless of different temperatures. We also find that the main products of CL20/BTF co-crystal are NO2, NO, NO3, HNO, O2, N2, H2O, CO2, N2O, and HONO, etc., on which the temperature forms certain influence.

催化油浆的热转化规律

以催化油浆作为实验对象,通过热反应实验对催化油浆的热反应性能进行研究,考察催化油浆热转化机理。研究表明,催化油浆的结焦率曲线与反应温度呈线性增加,不存在拐点,说明催化油浆不存在结焦诱导期,而且油浆中存在较易发生反应的组分。基于催化油浆热反应过程中四组分的变化规律,推测了催化油浆热反应机理:饱和分主要发生裂解反应;芳香分既可断侧链生成裂解产物,也可缩合生成胶质,进而生成沥青质、甲苯不溶物,最后生成焦炭;胶质优先发生裂解反应生成芳烃或其他裂解产物,后作为反应中间相存在;沥青质主要发生缩合反应生成焦炭,部分沥青质会发生断侧链生成裂解气。

Pyrolysis of D-Glucose to Acrolein

Despite of its great importance, the detailed molecular mechanism for carbohydrate pyrolysis remains poorly understood. We perform a density functional study with a newly developed XYG3 functional on the processes for D-glucose pyrolysis to acrolein. The most feasible reaction pathway starts from an isomerization from D-glucose to D-fructose, which then undergoes a cyclic Grob fragmentation, followed by a concerted electrocyclic dehydration to yield acrolein. This mechanism can account for the known experimental results.

Theoretical Study on Mechanism and Kinetics of Reaction of O（^3p） with Propane

The reaction of C3H8＋O（^3p）→C3HT＋OH is investigated using ab initio calculation and dynamical methods. Electronic structure calculations for all stationary points are obtained using a dual-level strategy. The geometry optimization is performed using the unrestricted second-order Moller-Plesset perturbation method and the single-point energy is computed us- ing the coupled-cluster singles and doubles augmented by a perturbative treatment of triple excitations method. Results indicate that the main reaction channel is C3Hs＋O（^3p）→i- C3HT＋OH. Based upon the ab initio data, thermal rate constants are calculated using the variational transition state theory method with the temperature ranging from 298 K to 1000 K. These calculated rate constants are in better agreement with experiments than those reported in previous theoretical studies, and the branching ratios of the reaction are also calculated in the present work. Furthermore, the isotope effects of the title reaction are calculated and discussed. The present work reveals the reaction mechanism of hydrogenabstraction from propane involving reaction channel competitions is helpful for the understanding of propane combustion.

Non-isothermal decomposition kinetics of hydrogarnet in sodium carbonate solution

Carbonation decomposition of hydrogarnet is a significant reaction of the calcification-carbonation new method for alumina production by using low-grade bauxite.In this work,non-isothermal decomposition kinetics of hydrogarnet in sodium carbonate solution was studied by high-pressure differential scanning calorimetry(HPDSC) at different heating rates of 2,5,8,10,15 and 20 K·min^(-1),respectively.The activation energy(E_α) was calculated with the help of isoconversional method(model-free),and the reaction mechanism was determined by the differential equation method.The calculated activation energy of this reaction was 115.66 kJ·mol^(-1).Furthermore,the mechanism for decomposition reaction is Avrami-Erofeev(n=1.5),and the decomposition process is diffusion-controlled.

Thermal catalysis under dark ambient conditions in environmental remediation:Fundamental principles, development, and challenges

Thermal catalytic degradation of organic pollutants conducted in the dark at room temperature under atmospheric pressure without the need of external chemicals and energy sources has attracted a lot of attention over the last two decades. It provides unparalleled advantages over other advanced oxidation processes (AOPs) in treating domestic and industrial contaminated wastewater from the viewpoint of energy/chemical conservation and ease of operation. Rich knowledge has been accumulated in terms of the synthesis and application of thermal catalysts though controversies remain regarding their underlying mechanisms. This review sheds light on the proposed thermo- catalysis mechanism for the first time and presents the development of thermal catalysts under dark ambient conditions with a focus on catalyst materials, catalytic activity, and mechanism. The present review aims to provide mechanistic insights into the rational design of novel and efficient catalysts, and their underlying mechanisms as well as the emerging challenges and perspectives in thermo-catalysis under dark ambient conditions used for the practical and efficient treatment of contaminated wastewater.

Pyrolysis Mechanisms of Quinoline and Isoquinoline with Density Functional Theory

The pyrolysis mechanisms of quinoline and isoquinoline were investigated using the density functional theory of quantum chemistry,including eight reaction paths and a common tautomeric intermediate 1-indene imine.It is concluded that the conformational tautomerism of the intermediate decides the pyrolysis products(C6H6,HC≡C—C≡N,C6H5C≡N and HC≡CH)to be the same,and also decides the total disappearance rates of the reactants to be the same,for both original reactants quinoline and isoquinoline during the pyrolysis reaction.The results indicate that the intramolecular hydrogen migration is an important reaction step,which often appears in the paths of the pyrolysis mechanism.The activation energies of the rate determining steps are obtained.The calculated results are in good agreement with the experimental results.

Research Progress of Palladium Catalysts for Methane Combustion

Recent research progress and development of the palladium catalysts for methane combustion are described in this study.The influence of active species,precursor,solvent,preparation methodologies,support and dopant on the catalytic activity and thermal stability of the palladium catalysts was discussed.Results of deactivation and poisoning of palladium catalysts were analyzed.Furthermore,possible kinetic models and reaction mechanism were indicated for Pd catalysts.

Efficient synthesis of 1,6-hexamethylene diurethane through coupling transesterification and methoxycarbonylation with methyl phenyl carbonate as intermediate

A reaction coupling system of transesterification and methoxycarbonylation with methyl phenyl carbonate （MPC） as intermediate was established to efficiently prepare 1,6-hexamethylene diurethane （HDU） from 1,6- bexametbylene diamine （HDA）. The feasibility of the system was explored using the thermodynamics analysis, the reaction mechanism and the experiment results. The optimal reaction was carried out to get higher HDU yield. The thermodynamic analysis showed that the metboxycarbonylation of HDA with MPC, the Gibbs free energy of which was negative, was a spontaneous process. Furthermore, the equilibrium constant of the methoxycarbonylation of HDA with MPC was much greater than that of the transesterification of dimethyl carbonate （DMC） with phenol, so the reaction coupling could be realized under mild conditions. The reaction mechanism analysis indicated that phenoxy anion was the key spedes for reaction coupling. Higher MPC concentration was detected when sodium phenoxide was used as transesterification reactant with DMC, since the phenoxy anion of sodium phenoxide could be dissociated more easily. Sodium pbenoxide was more suitable to prepare HHDU through reaction coupling. A yield of HDU as high as 98.3% could be reached under the optimal conditions of mPhONa/mDMC = 0.027 and nDMC/nHDa = 8/1 at 90 ℃ in 2 h.

Application of Thermal Cracking Mechanism of Chrysene Molecule Using Density Functional Theory

Density functional theory calculations were carried out to study the thermal cracking for chrysene molecule to estimate the bond energies for breaking C 10b-C 11, C 11-H 11 and C4a-C 12a bonds as well as the activation energies. It was found that for C 10b-C 11 C11-HI 1 and C4a-C12a reactions, it is often possible to identify one pathway for bond breakage through the singlet or triplet states. Thus, the C 11-H11 and C11-C10b bonds ruptured in triplet state whilst the C12a-C4a in singlet state. Also, it was fond that the activation energy value for C4a-C12a bond breakage is lower than required for C10b-C11 and C11-H11 bonds that enquired the C4a-C12a bond ＂bridge bond＂ is a weaker and ruptured firstly in thermal cracking process. It seems that the characteristic planarity for polyaromatic hydrocarbons is an important factor to acquire the molecule structure the required stability along the reaction paths as well as the full octet rule and Clar＇s n-sextet structure, especially when chrysene molecular lose the property of planarity. The atomic charges supported the observation that the breaking bonds C10b-C11, CI1-H11 and C4a-C12a in triplet or singlet states. The configurations in transition state and the conformation for the end products reaction were explained and discussed.

A new insight into electrochemical detection of eugenol by hierarchical sheaf-like mesoporous NiCo2O4

NiCo2O4 nanosheets with sheaf-like nanostructure morphologies have been synthesized by a facile one-step hydrothermal reaction followed by annealing treatment. Impressively, the NiCo2O4 nanosheets exhibit rapid detection of eugenol. The linear range of detection is from 1-500μM, and the limit of detection is 5.4 μM. The NiCo2O4 modified electrode demonstrated high sensitivity, good repeatability and reproducibility, and long-term stability （7% decrease in response over 30 days）. Based on this work, an electrochemical reaction mechanism for eugenol oxidation was proposed, and in addition, the NiCo2O4 modified electrode was successfully employed for the analysis of eugenol in medicative balm samples. Recovery values for eugenol in medicative balm samples were in the range 98.7%-105.5%.