OXO(X=Cl,Br)自由基与CO和NO自由基反应机理的理论研究

对CO和NO自由基与OXO(X=Cl,Br)自由基反应机理进行了理论研究.在MP2/6-311 +G(d,P)水平下优化了反应物、产物、中间体和过渡态的几何构型,并对所有平衡构型进行了简谐振动频率分析.在相同的计算水平下以过渡态为出发点,利用内禀反应坐标(IRC)理论得到了反应的最小能量路径(MEP),能量信息的进一步校正在较高的MCQCISD//MP2/6-311+G(d,p)水平下完成.研究结果表明,该反应体系可发生氧抽提反应,其中NO与OClO的反应是最具有动力学优势的.     

微细电火花加工微孔时加工作用力影响

在用微细电火花加工大深径比微孔的过程中发现,相同加工条件下工具电极越长则加工孔径越大.为了解释这一现象,采用经典Bernoulli-Euler杆件理论,针对加工作用力对电极变形影响的3种情况,对工具电极的变形量进行了求解,结果表明计算值与实验结果非常接近,从理论上揭示了加工作用力对微孔加工过程的影响.加工中随电极长度的...     

联结数与分数（k，n’）一临界消去图

设G是一个图,若删除G中任意n’个顶点的剩余子图依然是分数k-消去图,则称G为分数（k,n＇）-临界消去图．笔者证明了若k≥2,n,≥0,bind（G）≥^（n＇＋1）且6（G）≥k＋n＇＋1,则G是分数（k,n＇）-临界消去图．     

两种多糖甲基化方法的比较

对两种常见的多糖甲基化实验方法与结果做一个比较,结果显示：出同种等量的多糖在一次甲基化反应的前提下再结合改进后的甲基化方法比经典甲基化方法对多糖的甲基化要更充分,并由此从两种反应的反应历程对此实验结果进行解释.通过对反应历程的研究发现,改进后的甲基化方法反应中没有水生成,是多糖甲基化较为彻底的关键原因.由此表明由改进后的甲基化方法在多糖的一次甲基化成功率要比用经典甲基化方法的高,所以改进后的甲基化方法可以被运用在多糖结构的研究领域中.     

镁 － 镧复合氧化物固体碱催化甲醛、丁醛缩合制备 2，2 － 二羟甲基丁醛

以镁-镧复合氧化物为固体碱催化剂,首次用于甲醛、丁醛间的羟醛缩合反应．GC、GC—MS分析发现：2,2-二羟甲基丁醛为主产物,2-乙基丙烯醛为最主要的副产物．筛选Mg—Al复合氧化物、MgO和Mg．La复合氧化物3种固体碱,发现Mg-La复合氧化物具有最佳催化活性．当甲醛和丁醛摩尔比为2．5-1时,在50℃反应4h,丁醛转化率为75％、DMB选择性为37％、DMB得率为28％．催化剂可以循环使用4次,没有明显失活,有利于降低反应成本,减少环境污染．     

Formation and mechanical properties of Zr-based bulk metallic glass composites with high oxygen levels

Zr-based bulk metallic glass(BMG) composites with in situ formed Y 2 O 3 particle reinforcements were synthesized by proper additions of Y to ultrahigh-oxygen-containing glass-forming alloy precursors.Microstructures,thermal stabilities,and mechanical properties of the composites were investigated.Glass formation was greatly enhanced by Y additions in the alloys and the resultant particles were homogenously distributed in the glassy matrix,allowing for the fabrication of oxide dispersion strengthened BMG composites.The compressive strength and hardness increased by 10% and 20%,respectively,with the introduction of Y 2 O 3 particles.These results are significant for the design and production of Zr-based BMGs and BMG composites with improved properties using commercial high-oxygen content raw materials under industrial conditions.     

Efficient synthesis of functionalized 2-pyridones by ytterbium chloride catalyzed tandem condensation

An efficient method was developed for the synthesis of arylidene heterobicyclic 3-cyano-2-pyridones via ytterbium chloride catalyzed tandem condensation of aromatic aldehydes,cyclic ketones,and cyanoacetamide.The conditions and scope of the reaction were investigated and a reaction mechanism was proposed.     

Catalytic oxidation of phenol in wastewater-A new application of the amorphous Fe78Si9B13 alloy

The amorphous Fe78Si9B13 alloy was used as a heterogeneous Fenton catalyst in the process of phenol degradation.The influences of main operating parameters such as reaction temperature,catalyst amount,hydrogen peroxide dosage and initial pH of solution on phenol degradation rate were investigated.The maximum mineralization of phenol was achieved at 60°C,6 g/L Fe78Si9B13, 0.31 mol/L hydrogen peroxide,with an initial pH of 2.5.More than 99%of phenol was completely removed under the optimum conditions within 10 min for a solution containing 1000 mg/L of phenol.Batch experiments for solutions containing phenol con- centrations ranging from 50 to 2000 mg/L were investigated under the above conditions and the same excellent degradation rate was obtained.The Fe78Si9B13 showed better catalytic activity than iron powder and Fe 2+ .Addition of n-butannol(hydroxyl radical scavenger)decreased the degradation rate of phenol,which demonstrates that hydroxyl radicals were mainly responsible for the removal of phenol.We demonstrated that phenol may be degraded by hydroxyl radicals decomposed by hydrogen peroxide on the surface of Fe78Si9B13 and illustrated the reaction mechanism for this process.This amorphous alloy exhibited high stability in recycling experiments and showed excellent reuse performance even after continuous operations of 8 cycles.     

AlCl3催化1,1,1-三甲基-2,2,2-三氯二硅烷裂解的理论研究

结合采用DFT（B3LYP）及二级微扰方法对AlCl3催化1,1,1-三甲基-2,2,2-三氯二硅烷裂解反应的机理进行了研究.通过计算数据结果表明,此裂解反应为放热反应,理论产率比较高.反应可以同时按2种通道进行,其中通道2反应较为容易,其3步反应的焓变依次为：ΔH1（86.963 kJ.mol-1）,ΔH2（-237.596 kJ.mol-1）,ΔH3（-127.568 kJ.mol-1）.通道2的各步正反应活化能数值表明,第3步为速控步,其正反应的活化能E3为214.913 kJ.mol-1.     

α-乙酰基二硫缩烯酮在TiCl4催化下的酰化反应机理研究

在B3LYP/6-311G(p)理论水平上研究α-乙酰基二硫缩烯酮在TiCl4催化下的酰化反应的微观反应机理.优化反应过程中的反应物、中间体、过渡态和产物的结构,同时采用了极化连续介质模型(PCM)对各个驻点进行了单点能计算以模拟在CH2Cl2溶剂中的反应过程,并且应用了自然轨道理论(NBO)和分子中的原子理论(AIM)分析了这些物质的成键特征和轨道间的相互作用.计算结果得到此反应在TiCl4催化情况下的活化能小于没有催化剂情况下的活化能,证明了在TiCl4催化剂参加的情况下有利于此反应的进行,溶剂效应也较大程度地降低了此反应的活化能.