Kinetics of synthesis of Li_4Ti_5O_(12) through solid-solid reaction

Sohd-solid reaction under low heat or low temperature is an approach to synthesize various kinds of materials that were widely used in electrochemistry field. In this paper a theoretical treatment has been presented for analyzing the mechanism of sohd-solid reaction and deriving a series of formulae to describe the variation and rate of reactions. This new model has been used in the manufacturing of spinel Li4Ti5O12. The results show that this new model works very well and will play a useful role for guiding the manufacturing of electrochemical materials.

Solid-phase Synthesis of PNA Monomer by Ugi Four-component Condensation Reaction

Peptide nucleic acids (PNA) oligomers were synthesized in most cases by peptide synthesis from N-protected monomers. In this work a new method of obtaining PNA monomer by Ugi four-component condensation reaction was tested by solid-phase synthesis. The Fmoc protected PNA monomer was build up with thymin-1-yl acetic acid, 3-methylbutyl aldehyde, Fmoc protected aminoethyl isocyanide and Gly-Wang resin.

STUDIES ON THE REACTION OF SULFUR,SELENIUM AND TELLURIUM WITH SODIUM HYDROXIDE UNDER PHASE TRANSFER CATALYSIS(Ⅱ).A CONVENIENT METHOD FOR THE SYNTHESIS OF BI(ACYL)DISULFIDES

A simple and general method for the synthesis of bi(acyl)disulfides is reported.Sulfur is allowed to react with sodium hydroxide to give sodium disulfide at 65℃ under PTC,which can react with acyl halides to afford bi(acyl)disulfides in good to excellent isolated yields.The effects of solvents and phase transfer catalysts are discussed.

The Process of TiB_2-Cu Composite Phase and Structure Formation during Combustion Synthesis

The reaction process of combustion synthesis for TiB2 -Cu was investigated in detail using combustion-wave arresting experiment, X-ray diffraction （ XRD ） analysis, SEM analysis and differential thermal analysis （ DTA ）. The XRD analysis results for the different parts of the quenched specimen show that TiCux intermetallic phase firstly forms with the propagation of combustion wave, and then Ti1.87 B50 and Ti3B4 metastable phases come forth due to the diffusion of B atoms and finally the stable TiB2 phase forms because of the continuous diffusion of B atoms. The formation of TiB2 phase is uot completed by one step, but undergoes several transient processes. The process of reaction synthesis for Ti-B-Cu ternary system can be divided into three main stages： melting of Cu and Ti , and the formation of Cu- Ti melt and few TiCux , TiBx intermetallic phases ; large numbers of TiCux intermetallic phases formation and some fine TiB2 particles precipitation ; and the TiB2 particles coarsening and the stable TiB2 and Cu two phases formation in the final product.

Effect of chloralkanes on the phenyltrichlorosilane synthesis by gas phase condensation

To enhance the process of phenyltrichlorosilane synthesis using gas phase condensation, a series of chloralkanes were introduced. The influence of temperature and chloralkane amount on the synthesis was studied based on the product distribution from a tubular reactor. The promoting effect of chloralkane addition was mainly caused by the chloralkane radicals generated by the dissociation of C–Cl bond. The promoting effect of the chloromethane with more chlorine atoms was better than those with less chlorine atoms. Intermediates detected from the reactions with isoprene and bromobenzene demonstrated that both trichlorosilyl radical and dichlorosilylene existed in the reaction system in the presence of chloralkanes. A detailed reaction scheme was proposed.

Solid Phase Synthesis of 1,4-Disubstituted 1,2,3-Triazole from Polystyrene-supported Selenium Resin

We report here a solid-phase synthesis of 1, 4-disubstituted 1, 2, 3-triazole using polystyrene-supported selenium resin. The resin used here not only works as a simple linker, but also assists the crucial α-alkylation reaction and selenoxide syn-elimimation, which ensures the purity of the products.

Synthesis of Vitamin K_(2(10))

The Diels-Alder adduct, which is prepared from a phase transfer catalyzed reaction of menadione witb cyclopentadiene, was alkylated with geranyl chloride on sodium amide as a deproteined reagent to form the corresponding alkylation product, from which vitamin K2(10) is obtained by a retro-DielsAlder reaction.

An Efficient Synthesis of Cyclopeptides Bridged with Aliphatic-aryl Ether Bond

Based on the pseudo-dilution effect (PDE) on solid support, three cyclopeptides with an aliphatic-aryl ether bond as the bridge were synthesized via SN2 reaction between bromoacetylated at N-terminal and the phenol –OH group in C-terminal Tyr residue. All the products were obtained in good overall yields and characterized by related analytic data.

Synthesis Mechanism and High Temperature Chemical Stability of CaZrO3

CaZrO3 powder was prepared using CaO,CaCO3 and Ca(OH)2 as calcium source,nano m-ZrO2 powder,micron m-ZrO2 powder,micron CaO partially stabilized ZrO2(Ca-PSZ)powder as zircon source,through high temperature solid reaction.Effect of the calcination temperature(800,900,1000,1100,1200,1300,1400,1500,and 1600℃)and the holding time(3,4,and 5 h)on the phase composition change was studied to research the synthesis mechanism.The synthesized CaZrO3 powder was mixed with CaO,MgO,Al2O3,Cr2O3,SiO2,and ZrO2 powder separately and fired at 1500℃for 3 h to prepare specimens to research the high temperature chemical stability of CaZrO3 with different reaction mediums.The results show that during the synthesis process,the CaZrO3 content does not always increase with the increasing calcination temperature or the prolonging holding time,CaZrO3 decomposes resulting from the diffusion of Ca2+and O2-in CaZrO3 to m-ZrO2 or c-ZrO2.At high temperatures,when CaZrO3 is in alkaline environment(such as environment containing CaO or MgO),the high temperature chemical stability is high,but when CaZrO3 is not in alkaline environment(such as environment containing Al2O3,Cr2O3,SiO2 or ZrO2),the high temperature chemical stability is low.

Wittig反应实验的绿色化改进

传统的有机化学实验教学中,大多侧重实验技能的训练,设置实验内容时对实验安全性、经典性和可重复性等因素考虑较多,而对反应的绿色化、新方法和新技能等重视程度不够。为此,经典的有机反应也需要不断改进,本文将需要在大量有机溶剂中进行的传统Wittig反应改进为无溶剂的固相研磨反应,使得合成方法更加简单、绿色、安全和高效。设计合成了3个不同推拉型(D-π-A)二苯乙烯结构分子,优化了反应条件,测定了它们的光谱性质,并对其进行比较,讨论其构性关系,不仅引入绿色化学理念,而且对知识进行扩展,增加了实验的新颖性、探索性和趣味性,提升了学生创新能力。

温度在四氧化三钴制备中的影响分析

温度在四氧化三钴生产中是一个重要的控制因素,不稳定会导致粉末指标大的波动。采用两种温度工艺合成球形碳酸钴,利用XRD和TEM分析其生长机理,不同温度下呈现不同的优势生长面,高温下为多晶结构,低温单晶,通过SEM看高温碳酸钴表面颗粒呈棒状,低温为细颗粒堆叠。以低温合成的球形碳酸钴为原料,采用高温煅烧方法,制备球形四氧化三钴。系统研究了不同温度和不同升温速率下热性能、粒径、物相的变化。通过这些条件实验揭示了改变温度条件及不同升温速率下碳酸钴的生长规律及其内在分解原理。

Synthesis,formation mechanism,and intrinsic physical properties of several As/P-containing MAX phases

321 phases are an atypical series of MAX phases,in which A=As/P,with superior elastic properties,fea-turing in the MA-triangular-prism bilayers in the crystal structure.Until now,besides Nb 3 As 2 C,the pure phases of the other 321 compounds have not been realized,hampering the study of their intrinsic prop-erties.Here,molten-salt sintering(MSS)and solid-state synthesis(SSS)were applied to synthesize As/P-containing 321 phases and 211 phases.Analyzing the phase composition of the end-product via multiple-phase Rietveld refinement,we found that MSS can effectively improve the purity of P-containing MAX phases,with the phase content up to 99%in Nb_(3)P_(2)C and 75.4(5)%in Nb 2 PC.In contrast,MSS performed poorly on As-containing MAX phases,only 8.9(4)%for Nb 3 As 2 C and 64(2)%for Nb 2 AsC,as opposed to the pure phases obtained by SSS.The experimental analyses combined with first-principles calculations reveal that the dominant formation route of Nb_(3)P_(2)C is through NbP+Nb+C→Nb_(3)P_(2)C.Moreover,we found that the benefits of MSS on P-containing MAX phases are on the facilitation of three consid-ered chemical reaction routes,especially on Nb 2 PC+NbP→Nb_(3)P_(2)C.Furthermore,the intrinsic physical properties and Fermi surface topology of two 321 phases consisting of electron,hole,and open orbits are revealed theoretically and experimentally,in which the electron carriers are dominant in electrical trans-port.The feasible synthesis methods and the formation mechanism are instructive to obtain high-purity As/P-containing MAX phases and explore new MAX phases.Meanwhile,the intrinsic physical properties will give great support for future applications on 321 phases.

Effect of Pressure and Temperature on Phase Transformation and Properties of Titanium Aluminide Obtained through Reaction Synthesis

Reaction synthesis process has been used to develop γ titanium aluminide using elemental powders. Powder mixture of Ti-48 at. pct AI was prepared in ball mill and reaction synthesis was carried out in hot press with varying temperature and pressure. Titanium aluminide synthesized under high pressure and temperature resulted in better properties with respect to densification, homogenization response, mechanical properties and oxidation resistance as compared to that synthesized under low pressure and temperature. AI rich phases were observed in as-synthesized condition in all the experiments. However, some Ti rich phases were also found in high pressure-temperature synthesized samples. Density, hardness and tensile strength have been correlated with applied pressure through empirical relations. Variation in density with pressure is found to be logarithmic whereas hardness and tensile strength variation with pressure is polynomial.

Synthesis of well-defined functional crystals by high temperature gas-phase reactions

Over the past decades,there have been many synthesis methods on producing well-defined crystals,due to their enormous application potentials in industrial field.Among them,high temperature gas-phase reactions(HTGR)approach may be one of the most promising processes for fabrication of well-defined crystals with controllable structure,size,shape,and composition.This review is focused on the recent progresses in synthesizing well-defined crystalline TiO2dominated with,respectively,{001}facets and{105}facets,one-dimensional ZnO and SnO2nanorods/nanowires,MoS2nanosheets as well as GaP,InP,and GaAs nanowires via HTGR approach.Although these research works were currently carried out on experimental scale,it is worth to note that the industrial importance of this HTGR approach for design and fabrication of well-defined crystals in the future owing to its advantages of continuous and scalable production with controlled dimensions and low cost.

Multi-step Reaction Route Developed for Improving Crystallinity of Boron Nitride Nanoparticles

A multi-step reaction route was developed to synthesize boron nitride（BN） nanoparticles via the reactionbetween NaN3 and BC13 in a benzene-thermal solution. By means of this route, the crystallinity of BN nanoparticleswas improved via increasing the reaction steps. Meanwhile, a phase transformation from hexagonal BN（hBN） or tur-bostratic BN（tBN） to cubic BN（cBN） occurred, resulting in the increase of cBN content. Moreover, the content ofcBN also slightly increased when the temperature was elevated from 265 ℃ to 280 ℃.

免热处理(TiB_(2)+ZrB_(2))/Al-Mg-Mn基复合材料的显微组织与力学性能

基于交通、航空航天等领域高强韧精密复杂零件免热处理的需求,采用原位生成反应法制备了(TiB_(2)+ZrB_(2))/Al-Mg-Mn基复合材料,对比研究了重力铸造和挤压铸造制备的(TiB_(2)+ZrB_(2))/Al-Mg-Mn基复合材料的微观组织和力学性能。结果表明:原位生成反应法制备的复合材料中生成了大量纳米级的TiB_(2)和ZrB_(2)颗粒。拉伸实验结果表明,挤压铸造复合材料试样的抗拉强度、屈服强度和伸长率分别为296 MPa、185 MPa和12.2%,这些参数比重力铸造成型的Al-Mg-Mn合金分别提高了57%、95%和40%;比重力铸造复合材料分别提高了12%、11%和36%。分析发现,复合材料相比无添加Al-Mg-Mn合金强韧性能更高的原因在于TiB_(2)和ZrB_(2)颗粒协同增强细晶强化作用;而挤压铸造成型的复合材料的力学性能优于重力铸造成型的复合材料的主要原因在于挤压力所致的晶粒细化和Orowan强化作用。

电催化硝酸盐还原合成氨电势相关性的计算见解

人类活动和工业生产导致全球氮循环严重失衡,对生命系统的健康造成了一定威胁.因此,开发高效、环保的NO_(x)脱除技术具有重要意义.其中,电化学硝酸盐还原反应(eNO_(3)RR)是反向人工氮循环的重要组成部分,同时也被认为是一种非集成式合成氨(NH_(3))的可行途径.NH_(3)是生产肥料的重要原料之一,传统哈伯法(H-B)合成氨能耗高,且会排放大量温室气体CO_(2),由可再生电力驱动的电催化氮气还原(eNRR)合成氨被认为是一条更环保和可持续的路线.目前,一些研究表明电催化硝酸盐还原具有比eNRR更高的产氨活性和选择性.然而,一个主要的挑战是在低过电位下产物的选择性,即亚硝酸盐(HNO_(2))和NH_(3)之间的竞争.本文选择了六个具有MN_(4)单元的石墨烯负载的过渡金属单原子催化剂(SACs)作为模型,通过密度泛函理论(DFT)计算研究eNO_(3)RR机理.采用本课题组开发的反应相图分析(RPD)方法从全局热力学最优的角度构建了六个MN_(4)催化剂的二维准活性和选择性相图,其中FeN_(4)催化剂展示出较高的准活性和适当的选择性.DFT计算结果表明,产生HNO_(2)和NH_(3)的最优路径共享一个关键中间体(NO_(2)*),其吸附结构和在后续转化中的偏好决定了产物选择性.结合电势相关性动力学势垒计算和微观动力学模拟结果,动力学研究表明,理论上两种产物不同电压下的法拉第效率(FE)趋势会发生反转,与FeN_(4)催化剂上实验测得的HNO_(2)和NH_(3)的FE趋势和反转电压吻合,这归因于两个重要的基元步骤(R4:NO_(2)*-→cisHNO_(2)*和R7:NO_(2)*→HNO_(2)+*)具有不同的电荷转移系数(β),前者(R4)具有更大的电荷转移系数,使得生成NH_(3)的动力学能垒随电压的降低而下降得更快,这就把NH_(3)从低过电势下的低选择性到高过电势下的高选择性归因到动力学问题,较好地理解了两种产物的FE发生发转的原因.最后,从电子结构方面对R4和R7两个关键基元步骤的初态和过渡态进行了电子局域化函数和晶体轨道哈密顿布居分析.综上,理论计算的机理研究很好地解释实验观察的结果,其机理方面的理解对于将来理性设计高效的eNO_(3)RR合成NH_(3)催化剂具有一定的指导意义.

二苯甲醇制备实验的改进

在国内有机化学实验教材中,制备类实验多数采用液相合成.与之相比,固相合成具有高效、安全和绿色环保等优势.因此,拓展固相反应在基础有机化学实验教学中的应用具有重要意义.以二苯甲醇的制备实验为例,探究固相反应可行性.反应过程避免使用毒性有机溶剂并采用温和型还原剂叔丁基胺硼烷,既降低了反应的毒性又增加了操作的安全性.实验操作简单,反应过程加上后处理步骤只需1.5小时,二苯甲醇的分离产率可达86%.此外,在实验过程中引入TLC、GC-MS和NMR等手段对产物进行分析表征,有利于提升学生的综合实验技能和科学素养.

A New Solution-phase Parallel Synthesis of 2-Alkylamino-3-aryl-5-phenylmethylene-3,5-dihydro-4H-imidazol-4-ones

Thirteen new 2 alkylaminoimidazolones (4) were rapidly synthesized by a new solution phase parallel synthetic method, which includes aza Wittig reaction of iminophosphorane (1) with aromatic isocyanate to give carbodi imide (2) and subsequent reaction of 2 with various aliphatic primary amine in a parallel fashion. The products were confirmed by 1H NMR, MS, IR and X ray crystallographic analysis. The unusual selectivity of the cyclization was probably due to the geometry of the guanidine intermediate.

Synthesis of Iron-Carbide Nanoparticles:Identification of the Active Phase and Mechanism of Fe-Based Fischer-Tropsch Synthesis

Despite the extensive study of the Fe-based Fischer-Tropsch synthesis(FTS)over the past 90 years,its active phases and reaction mechanisms are still unclear due to the coexistence of metals,oxides,and carbide phases presented under realistic FTS reaction conditions and the complex reaction network involving CO activation,C-C coupling,and methane formation.To address these issues,we successfully synthesized a range of pure-phase iron and iron-carbide nanoparticles(Fe,Fe_(5)C_(2),Fe_(3)C,and Fe_(7)C_(3))for the first time.By using them as the ideal model catalysts on high-pressure transient experiments,we identified unambiguously that all the iron carbides are catalytically active in the FTS reaction while Fe_(5)C_(2) is the most active yet stable carbide phase,consistent with density functional theory(DFT)calculation results.The reaction mechanism and kinetics of Fe-based FTS were further explored on the basis of those model catalysts by means of transient high-pressure stepwise temperature-programmed surface reaction(STPSR)experiments and DFT calculations.Our work provides new insights into the active phase of iron carbides and corresponding FTS reaction mechanism,which is essential for better iron-based catalyst design for FTS reactions.