李欢
,
陈光需
,
Paul N.Duchesne
,
张鹏
,
代燕
,
杨华艳
,
吴炳辉
,
刘圣洁
,
许潮发
,
郑南峰
催化学报
doi:10.1016/S1872-2067(15)60930-5
负载型的金属催化剂虽然分离方便，但在反应活性、选择性以及催化剂的结构表征方面均明显不如相应的均相催化剂。将均相催化剂通过不同的化学键固载于高比表面积载体是实现均相催化剂多相化的重要途径，这样可使催化剂兼具均相和多相催化剂的优势。然而要将均相催化剂锚定于特定载体上，通常涉及较为复杂的合成反应，对载体也有严格的要求。因而该法仅仅适用于实验室研究，难以实现规模生产。因此，提供一种简便有效地制备兼具均相和多相催化剂优势的催化剂合成方法非常必要。本文报道一种简便的制备聚乙炔纳米颗粒负载Pd(II)催化剂(NP-Pd(II))的方法，所制催化剂在水相中的Suzuki-Miyaura偶联反应中表现出极高的活性，同时具有便于分离、容易放大制备的特点。在室温下，将乙炔气通入PdCl42-的水溶液中迅速变得浑浊，静置后容器底部有棕色沉淀，同时溶液变为无色透明。固体产物使用水、乙醇等溶剂进行洗涤；干燥之后收集既得聚乙炔纳米颗粒负载的Pd(II)催化剂NP-Pd(II)。使用透射电子显微镜、红外(IR)及拉曼吸收光谱、X射线衍射(XRD)、X射线光电子能谱(XPS)以及X射线吸收光谱(EXAFS)等手段对NP-Pd(II)进行了详细表征。结果显示，在NP-Pd(II)中Pd并非以Pd纳米颗粒形式存在； XRD中没有未Pd纳米晶的特征衍射峰。 IR等表征证明乙炔在Pd的催化作用下发生聚合作用，生成了聚乙炔。 EXAFS结果表明， Pd分别和氯原子以及C=C双键进行配位；同时，没有观察到Pd–Pd键的生成，进一步证明了Pd未被还原为Pd纳米颗粒。 XPS也印证了Pd(II)的价态。形貌上， NP-Pd(II)为直径2–3nm的颗粒，其中的Pd原子均匀分散于聚乙炔纳米颗粒上，使其在反应过程中能够充分地与底物接触，从而在Suzuki-Miyaura偶联反应中表现出极高的活性。更重要的是，由于“憎水效应”， NP-Pd(II)在溶液中以微米级的聚集体形式存在，因而反应后通过离心或者静置从反应体系中分离出来。因此，在NP-Pd(II)催化剂中，每个Pd原子都是潜在的活性中心，这与典型的均相催化剂相似；同时，其独特的形貌使其具备了多相催化剂便于分离的特点。因此， NP-Pd(II)是一种兼具均相和多相催化剂优点的催化剂且其催化剂的制备方法极为简便。乙炔是常用的工业气体，溶剂采用水，制备在室温下即可完成，我们也成功地制备出克级规模的高活性、稳定性的NP-Pd(II)催化剂。
关键词:
Suzuki偶联
,
乙炔
,
钯配合物
,
水性反应
邬云文
,
海文华
量子电子学报
doi:10.3969/j.issn.1007-5461.2006.05.011
运用熟知的级数截断方法,设计程序计算了线性Paul阱中两离子量子门系统Schr(o)dinger方程的精确解,分析了质心波函数几个较低能级的态,并作出对应的几率分布图;计算相对距离的方均差△r2＞(h)/2,相对运动的动量方均差△p2＜(h)/2,并满足量子力学的Heisenberg不确定度关系△r.△p＞(h)/2,它满足压缩态的条件,即质心处于基态时,两离子相对位置的量子态是一个压缩态,并得到了两离子纠缠态的表达式.纠缠的存在对量子计算和量子信息有影响,量子测量的不确定度和纠缠是在实验中应加以考虑的问题.
关键词:
量子信息
,
Paul阱
,
两离子
,
纠缠
,
量子态
Y.B. Hou
金属学报(英文版)
In this paper, the PMMA films doped with N,N'-diphenyl-N,N'-di(m-tolyl)-benzidineand rubrene were fabricated by spin coating, and the effect of photooxidation onthe photoluminescence of the doped PMMA thin films was investigated. The resultsshowed that under the irradiation of 350nm UV light, N,N'-diphenyl-N,N'-di(m-tolyl)-benzidine can sensitized rubrene and results in the enhancement in the photooxrationof rubrene. The effect of photooxidation on the photoluminescence from rubrene w asmore obvious. Both lifetime measurement and in situ measurement of photolumines-cence showed that rubrene molecules exist in two chemical surroundings.
关键词:
photoluminescence
,
null
Ceramics International
The dispersion behavior of Si3N4 nanopowders prepared by laser-induced gas-phase reaction in a non-aqueous solvent, N-N-dimethylformamide (DNIF) was studied, and triethanolamine (TEA) was selected as a dispersant. One hundred and sixty-six-day sedimentation tests were used to study the stability of the suspensions. Photon correlation spectroscopy was employed to measure the sizes of aggregates and coagulation rates. TEA was proved an effective dispersant for nano-Si3N4 in DMF, presoaking treatment could enhance the effect of the dispersant. TEA 1.0 wt.% referred to Si3N4 and a 1-month-presoaking gave the best dispersion, the dispersion stability was improved from several minutes to several months, and the average size of the aggregates was reduced to about a twenty-fifth. The dispersion ability of TEA was believed being related to its strong affinities both to the powder surface and to the solvent. (C) 2002 Elsevier Science Ltd and Techna S.r.l. All rights reserved.
关键词:
Si3N4;dispersion;nanopowders;N-N-dimethylformamide;triethanolamine;composite;powders
Journal of Magnetism and Magnetic Materials
We present first-principles study on the magnetic properties of the 3D metal-ligand coordination polymer [Cu(mal)(DMF)]n within the framework of density functional theory ( DFT) by using the full-potential linearized augmented plane-wave (FP-LAPW) method. The total and partial density of states ( DOS), the band structure, and the atomic spin magnetic moment of [ Cu( mal)( DMF)] n are calculated. The calculation reveals that [ Cu( mal)( DMF)] n is a ferromagnetic semiconductor. The calculated spin magnetic moment is about 1.000 mu B per molecule, which is in agreement with experimental value. (c) 2007 Elsevier B.V. All rights reserved.
关键词:
first-principles;electronic structure;ferromagnetic properties;complexes;acid
