Mechanism in homogeneous catalysis; NMR as a prime mover

An overview of the contribution of NMR to the development of our understanding of homogeneous catalysis is presented, with an emphasis on work from the author’s research group.     

RPS增容LDPE／PS研究

用ＨＡＡＫＥ、ＤＳＣ、ＩＲ等方法研究了侧基含有过氧键的反聚苯乙烯与ＬＤＰＥ之间的反应，并将其应用到ＬＤＰＥ／ＰＳ共混体系。考察了不同添加方式，交联助剂等对共混物力学性能、流变性能及微观结构的影响。     

Influence of silicon on the microstructure and mechanical properties of Zr-Si-N composite films

A series of Zr-Si-N composite films with different Si contents were synthesized in an Ar and N₂ mixture atmosphere by the bi-target reactive magnetron sputtering method. These films’ composition, microstructure and mechanical properties were characterized by energy dispersive spectroscopy, X-ray diffraction, scanning electron microscopy, atomic force microscopy and nanoindentation. Experimental results revealed that after the addition of silicon, Si₃N₄ interfacial phase formed on the surface of ZrN grains and prevented them from growing up. Zr-Si-N composite films were strengthened at low Si content with the hardness and elastic modulus reaching their maximum values of 29.8 and 352 GPa at 6.2 at% Si, respectively. With a further increase of Si content, the crystalline Zr-Si-N films gradually transformed into amorphous, accompanied with a remarkable fall of films’ mechanical properties. This limited enhancement of mechanical properties in the Zr-Si-N films may be due to the low wettability of Si₃N₄ on the surface of ZrN grains.     

Microstructure array on Si and SiOx generated by micro-contact printing, wet chemical etching and reactive ion etching

A method, combining micro-contact printing (μCP), wet chemical etching and reactive ion etching (RIE), is reported to fabricate microstructures on Si and SiOx. Positive and negative structures were generated based on different stamps used for μCP. The reproducibility of the obtained microstructures shows the methodology reported herein could be useful in Micro-Electro-Mechanical Systems (MEMS), optical and biological sensing applications.     

F+H2→HF+H反应的全量子态分辨的散射动力学研究

利用高灵敏度的氢原子里德堡飞渡时间谱方法研究了 F H_2→HF H 反应碰撞能在5.02kJ/mol 下的交叉分子束反应态态散射动力学.所有在时间飞渡谱中被观测到的谱峰可以归属为 HF 产物的振转态结构.还观测到了明显的 HF(v’=3)前向散射,以及少许的 HF(v’=2)前向散射.     

Optical properties of In2O3 oxidized from InN deposited by reactive magnetron sputtering

Unintentionally doped and zinc-doped indium nitride (U-InN and InN:Zn) films were deposited on (0 0 0 1) sapphire substrates by radio-frequency reactive magnetron sputtering, and all samples were then treated by annealing to form In₂O₃ films. U-InN and InN:Zn films have similar photon absorption characteristics. The as-deposited U-InN and InN:Zn film show the absorption edge, ∼1.8-1.9 eV. After the annealing process at 500 °C for 20 min, the absorption coefficient at the visible range apparently decreases, and the absorption edge is about 3.5 eV. Two emission peaks at 3.342 eV (371 nm) and 3.238 eV (383 nm) in the 20 K photoluminescence (PL) spectrum of In₂O₃:Zn films were identified as the free-exciton (FE) or the near band-to-band (B-B) and conduction-band-to-acceptor (C-A) recombination, respectively.     

多组分单体接枝聚丙烯/尼龙6反应共混物结晶行为研究

用多组分熔融接枝的方法将甲基丙烯酸缩水甘油酯 (GMA)和苯乙烯 (St)共同接枝到聚丙烯 (PP)上 ,制得具有较高GMA接枝率的多单体接枝聚丙烯 ,PP g (GMA co St) .将PP g (GMA co St)与尼龙 6 (PA6 )进行共混 ,利用扫描电镜 (SEM) ,差示扫描量热计 (DSC)和广角X射线衍射 (WAXD)对共混物的形态和结晶进行了研究 .在共混过程中 ,PP g (GMA co St)与PA6反应原位生成了PP g PA6 ,有效改善了共混物的相容性 ,分散相尺寸明显减小 .在PP g (GMA co St) PA6为 3 7的体系中 ,PP g (GMA co St)出现分级结晶现象 ,其在较低温度下的结晶属于均相成核结晶 .在PP g (GMA co St) PA6为 7 3的体系中 ,由于PA6相分散细微 ,在通常结晶温度下不结晶 ,而是在低温下均相成核与PP g (GMA co St)同时结晶 .WAXD证实体系中接枝PP ,PA6为分别结晶 ,无共晶或新的晶型产生     

四种硝基苯的电化学行为及其反应活性的理论计算

在滴汞电极上研究了硝基苯、对硝基甲苯、间二硝基苯及2，4-二硝基氯苯的电化学行为，并用量子理论对四种硝基苯化合物的反应活性进行了预测，理论与试验结果基本一致，据此提出了预测分子的电化学活性的方法。     

正丁基锂四氢呋喃引发α-甲基苯乙烯阴离子平衡聚合动力学及反应机理研究

本文研究了以正丁基锂为引发剂,四氢呋喃为添加剂,环己烷为溶剂中的α-甲基苯乙烯阴离子平衡聚合动力学。讨论了体系中的反应活性种;提出了聚合机理;得到了聚合温度为20℃时的平衡单体浓度与活性种速率常数及添加剂浓度之间的关系式。     

Facile preparation of organozinc bromides using electrogenerated highly reactive zinc and its use in cross-coupling reaction

Highly reactive zinc was readily prepared by electrolysis of a DMF solution containing pyrene as a mediator with a platinum cathode and a zinc anode. Preferential reduction of pyrene occurred to generate the corresponding radical anion, which reduced zinc ions generated from anodic dissolution to give zero valent zinc with high reactivity. The reactive zinc was successfully used for an efficient transformation of bromoalkanes into the corresponding organozinc bromides. Organozinc bromides obtained were further used successfully in Pd-catalyzed cross-coupling reaction with various aryl iodides and bromides.