杂多阴离子[GeMo12O40]4-α/β异构体的密度泛函研究

采用密度泛函方法，在DND基组水平上，对[GeMo12O40]^4-杂多阴离子最常见的α和β异构体进行了几何构型优化，得到了与X射线晶体衍射实验结果相一致的结构参数，并在此基础上进行了振动频率分析，得到了杂多阴离子的电子结构、热力学特性和振动光谱，通过定义α，β异构体异构化反应的Gibbs函变△Gα-β与温度的关系，研究了这两种异构体的相对稳定性．结果表明：低温时α异构体更稳定，高温时β异构体更稳定些，550K左右为转变点．振动频率分析得到2种异构体的最强峰位于4个频率位置，分别指认为vax(Mo-Od)，vas(Mo-Od)，vas(Mo-Oc-Mo)，vas(Ge-Oa)，vas(Mo-Ob-Mo)振动，与红外光谱(IR)的特征振动峰相对应，观察到了特征频率的振动模式，从理论计算角度说明了Rocchiccioli—Deltcheff关于振动模式的设想是合理的．     

新材料的发展与分析化学

文章介绍了新材料的重要性及发展方向,分析化学在新材料研制中起着耳目的作用,另一方面新材料也为分析化学的进展提供了课题与条件。微量分析、微区分析、表面分析是此领域中的重点。在未来的发展中,分析化学在材料的发展中的地位不会改变,并期待着分析灵敏度与空间分辩率的进一步提高。     

丙烯选择氧化铋钼铁复氧化物催化剂组成,结构及性能的研究

采用XRD、Raman、XPS及催化剂性能评价等手段,考察了Bi_3(FeO_4)(MoO_4)_2和Fe_2(MoO_4)_3分别存在及两者共存时对Bi-Mo复氧化物体系催化性能的影响.结果表明,这两种含Fe物种的存在都有助于改善Bi-Mo系复氧化物催化剂对丙烯选择氧化反应的催化性能.但两者在作用机理上有所不同.Fe_2(MoO_4)_3本身无催化活性,但在反应条件下可部分还原为FeMoO_4形成Fe~(3+)/Fe~(2+)氧化还原对;且其地结构上与α-Bi_2(MoO_4)_3相匹配,这些因素都有助于促进催化体系中电子和氧物种的传递及催化剂表面活性中心的再生,从而提高催化性能.Bi_3(FeO_4)(MoO_4)_2在反应条件下也可形成Fe~(3+)/Fe~(2+)氧化还原对,但由于其Fe~(3-)所处的化学环境与Fe_2(MoO_4)_3很不相同,且Fe的含量也不及Fe_2(MoO_4)_3,因此它在促进催化体系中电子和氧物种的传递及催化剂表面活性中心的再生等方面的性能较差,但它对提高催化剂表面的活性中心(Bi-Mo对)数目有贡献.     

Y2O3 and MgO co-doped ceria based electrolytes

Electrolytes of Ce_1-x-y Y _x Mg _y O_2-0.5x-y were prepared with citrate method and were characterized by inductively coupled plasma-atomic emission spectrometry, energy dispersive spectrometry, powder X-ray diffraction, and impedance spectroscopy. The effect of composition on the structure, conductivity, and stability of the electrolytes were investigated. When 0≤x≤ about 0.2 and 0≤y≤ about 0.05, the electrolytes were all single phase materials of ceria-based solid solution. However, when y> about 0.05, the electrolytes became two-phase materials, Y³⁺ and Mg²⁺ co-doped ceria-based solid solution and free MgO. The sample with nominal composition of Ce_0.815Y_0.065Mg_0.12O_2-d showed ionic conductivity at 973 K close to or even a little higher than that of similarly prepared Ce_0.9Gd_0.1O_1.95, but had lower cost of raw materials and a little better stability in reducing atmosphere. The existing of free MgO improved the stability of the electrolytes in reducing atmosphere, but too much free MgO reduced the conductivity.     

Aerobic oxidation assisted by ligand-free palladium catalysts

Aerobic oxidation of electron-rich benzylic and phenyl allylic alcohols was achieved with high yields with only 0.1 mol.% of Pd(OAc)2 catalyst in the absence of any ligand. This procedure was expected to be valuable for realistic industrial-scale applications from both economic as well as environmental points of view.     

酞菁铜与Q-CdS超微粒子界面的光致电荷转移研究

半导体超微粒子与有机分子界面的光致电行转移过程是当前光化学和材料科学研究的一个活跃领域［‘，2］；研究的目的主要有两个方面，一是研究半导体超微粒子表面光致电行转移的特性；二是研究有机分子对超微粒子的光敏化作用．目前，超微粒子的功能化研究日益深入，其独特的光     

Simulation of water cluster assembly on a graphite surface

The assembly of small water clusters (H2O)n, n = 1-6, on a graphite surface is studied using a density functional tight-binding method complemented with an empirical van der Waals force correction, with confirmation using second-order M?ller-Plesset perturbation theory. It is shown that the optimized geometry of the water hexamer may change its original structure to an isoenergy one when interacting with a graphite surface in some specific orientation, while the smaller water cluster will maintain its cyclic or linear configurations (for the water dimer). The binding energy of water clusters interacting with graphite is dependent on the number of water molecules that form hydrogen bonds, but is independent of the water cluster size. These physically adsorbed water clusters show little change in their IR peak position and leave an almost perfect graphite surface.     

活性炭和石墨混合载体的Pt催化剂（Pt/CG）对乙醇氧化电催化活性的影响

用化学沉积法制备炭载Pt(Pt/C)和以活性炭与石墨作混合载体的Pt(Pt/CG)催化剂。实验结果表明，活性炭与石墨质量比影响Pt/CG催化剂对乙醇氧化的电催化活性。当活性炭与石墨的质量比为15∶1时，制得的Pt/CG催化剂对乙醇氧化的电催化活性最高。     

NITROXIDE-MEDIATED FREE RADICAL SYNTHESIS OF MESOGEN-JACKETED LIQUID CRYSTAL POLYMERS*

The first TEMPO-mediated "living" free radical polymerization of liquid crystallinemonomer, 2, 5-bis[(4-methoxyphenyl)oxycarbonyl]styrene(MPCS), was carried out at 130℃ withBPO as an initiator. The molecular weight of the polymer can be varied from rather low values to highvalues while maintaining narrow polydispersity. It was observed that the polymerization of MPCSproceeded much faster than that of styrene. A tentative explanation for this fast polymerization wassuggested.