Synthesis,characterization, fluorescence and redox features of new <Emphasis Type="Italic">vic</Emphasis>-dioxime ligand bearing pyrene and its metal complexes

A new vic-dioxime ligand, N,N′-bis(aminopyreneglyoxime) (LH₂), and its copper(II), nickel(II) and cobalt(II) metal complexes were synthesized and characterized by elemental analyses, IR, UVVIS and ¹H and ¹³C NMR spectra (for the ligand). Mononuclear complexes were synthesized by a reaction of ligand (LH₂) and salts of Co(II), Ni(II), and Cu(II) in ethanol. The complexes have the metal-ligand ratio of 1: 2 and metals are coordinated by N,N′ atoms of vicinal dioximes. The ligand acts in a polydentate fashion bending through nitrogen atoms in the presence of a base, as do most vic-dioximes. Detection of a H-bonding in the Co(II), Ni(II), and Cu(II) complexes by IR revealed the square-planar MN₄ coordination of mononuclear complexes. Fluorescent properties of the ligand and its complexes arise from pyrene units conjugated with a vic-dioxime moiety. Fluorescence emission spectra of the ligand showed a drastic decrease in its fluorescence intensity upon metal binding. The electrochemical properties of the complexes were studied by the cyclic voltammetry technique. The nickel complex displayed an irreversible oxidation process while the copper complex exhibited a quasi-reversible oxidation and reduction processes based on the copper Cu(II)/Cu(III) and Cu(II)/Cu(I) couples, respectively.     

不锈钢基/β-PbO2-TiO2-Co3O4复合镀层制备及其性能表征

使用直流复合电沉积方法制备不锈钢基β-PbO2、TiO2掺杂β-PbO2、Co3O4掺杂β-PbO2、TiO2和Co3O4共掺杂β-PbO2复合镀层材料.采用SEM、EDS、XRD和电化学测试等对复合电极进行形貌、成分、组成和催化活性表征,并且将不锈钢基/β-PbO2-TiO2-Co3O4电极应用到锌电积实验中.结果表明,添加Co3O4能提高PbO2电极的催化活性;添加TiO2可以起到细化晶粒,增大比表面积的作用;不锈钢基β-PbO2-TiO2-Co3O4复合镀层阳极与Pb-Ag合金阳极相比,锌电积槽电压降低为2.97V,电流效率提高到91.2％,使用寿命延长.     

溶剂热法合成花朵状钴磁性粉体及表征

采用一种简单的溶剂热法成功的合成了花朵状的钴磁性粉体。通过X射线粉末衍射(XRD),扫描电子显微镜(SEM)等对样品进行物相与形貌的表征。结果表明样品为六排堆积(hcp)和面心立方结构(fcc)混合结构的钴单质,形貌为由很多个厚度约为50～150 nm的菱形花瓣构成的花朵状结构,每个花朵的尺寸约为2μm左右。采用振动样品磁强计(VSM)测试了样品的磁性能,测试表明样品在室温下表现出铁磁性,饱和磁化强度(Ms)为140 emu.g-1,剩磁(Mr)为9.4 emu.g-1,矫顽力(Hc)为280 Oe。     

Co3O4/CeO2的氧化还原性能及反应条件对其CO氧化活性的影响

采用沉淀氧化法制备了Co₃O₄/CeO₂催化剂。运用XRD、BET和TPR表征手段,考察了不同钴铈比及焙烧温度对钴铈复合氧化物物理及化学性能的影响,并分别在干、湿条件下进行了一氧化碳氧化反应研究。结果表明,与纯的Co₃O₄相比,在不同比例的Co₃O₄/CeO₂均经723 K焙烧的各种催化剂中,钴铈原子比为9∶1的复合氧化物粒径较小,比表面积较大,说明适当比例铈的添加能使Co₃O₄具有较小的粒径。此氧化物经538 K温度焙烧制得的钴铈比为9∶1的复合氧化物中Co₃O₄平均粒径为7.2 nm, BET比表面积为167.6 m²/g。经TPR考察发现其具有最优的氧化还原性能。     

ICP-AES法测定红土镍矿中镍、钙、钛、锰、铜、钴、铬、锌与磷的含量

建立了ICP-AES法测定红土镍矿中Ni;Ca;Ti;Mn;Cu;Co;Cr;Zn和P含量的方法。样品用HCl、HNO3溶解,加入HF和HClO4,加热至HClO4烟冒尽,用HCl溶解盐类,过滤,采用ICP-AES法同时测定滤液中Ni、Ca、Mn、Cu、Co、Zn、P;残渣经灼烧、挥硅、K2S2O7熔融、HCl浸取,所得溶液与滤液合并,测定溶液中Cr和Ti含量。方法检出限:P为0.022μg/mL,其它元素在0.0032～0.0085μg/mL之间,方法的精密度(n=7)在1.4%～2.9%之间。分析结果与分光光度法、XRF法和AAS法分析结果的相对误差:Ni、Cu、Co、Cr小于5%,Ti和Mn小于10%,Zn小于15%,Ca和P小于19%。     

可见光响应的CO3(PO4)2/Ag3PO4纳米复合光催化剂的制备及表征

采用简单的化学偏聚法合成出Ag3PO4纳米颗粒、磷酸钴(Co3(PO4)2,CoP)纳米片以及它们两者的纳米复合结构(CoP/Ag3PO4),同时还比较了它们的可见光催化活性.采用场发射扫描电镜(FESEM)、X射线衍射(XRD)、紫外-可见(UV-Vis)吸收光谱以及光致发光谱等手段对其形貌、结构、光学以及可见光催化性能等进行表征.结果表明,CoP/Ag3PO4复合纳米结构的可见光降解甲基橙(MO)的速率和循环稳定性均明显优于其它两种物质.这表明CoP应该起着共催化剂的作用,它能够抑制光生电子与空穴之间的复合,并且提供大量高活性的光生空穴.此外,我们还发现CoP/Ag3PO4降解另一种阳离子型染料——罗丹明B(RhB)的能力则远不如纯Ag3PO4,这可能是与光催化剂的表面性质发生改变有关,造成更低的RhB吸附能力.本文提供了一种廉价制备高效可见光催化剂的新方法.     

Pd–Co bimetallic nanoparticles supported on graphene as a highly active catalyst for Suzuki–Miyaura and Sonogashira cross-coupling reactions

Graphene (G) supported Pd–Co bimetallic nanoparticles (NPs) as a highly active catalyst was prepared by a chemical reduction method and used for coupling reactions. With the characterization of X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, and Raman spectrum, the composition of resulting Pd–Co material was identified to be alloy structural. The Pd–Co (1:1)/G exhibited the highest catalytic activity for the Sonogashira-type coupling reactions and also exerted satisfied catalytic activity and recycle stability for Suzuki–Miyaura cross-coupling reactions. This Pd–Co/G material also possessed other advantages such as low-cost, easy recycled from reaction system by a magnet for their magnetic property, and easy experimental handling.     

自组装DNA与[Co(phen)3]2+/3+相互作用的表面增强拉曼光谱法研究

对金基体上自组装ssDNA及dsDNA与钴邻菲啉配合物离子([Co(phen)3]2+/3+)相互作用进行电化学现场表面增强拉曼光谱(SERS)研究,获得相互作用位点及相互作用模式的信息.dsDNA与[Co(phen)3]2+/3+存在一定的嵌插作用,即配合物通过配体邻菲啉(phen)环以嵌插模式结合在碱基A-T及G-C富集区,同时与磷酸二酯键PO2结合,并伴随dsDNA螺旋构象由B型向A型转变;而[Co(phen)3]2+/3+则是以静电模式与ssDNA的磷酸二酯键PO2及脱氧核糖组成的骨架相互作用.     

载气气氛对Co/MgMoO4催化剂CVD法高效合成碳纳米材料的影响

High yield and quality mutli-walled carbon nanotube (MWNT) bundles and carbon nanofibers were synthesized by catalytic decomposition of methane over Co/MgMoO₄ catalyst at 1 000 ℃. TEM studies showed that the products were mainly carbon nanofibers without carrier gas and were all MWNT bundles with hydrogen or nitrogen as carrier gas. Thermal gravimetric analyses (TGA) on the raw product indicated that the purity of MWNT was higher than 95wt%. The growth mechanism of carbon nanofibers and MWNTs was also discussed.     

Particle size effects in Fischer-Tropsch synthesis by Co catalyst supported on carbon nanotubes

The effect of Co particle size on the Fischer-Tropsch synthesis (FTS) activity of carbon nanotube (CNT)-supported Co catalysts was investigated. Microemulsion (using water-to-surfactant molar ratios of 2 to12) and impregnation techniques were used to prepare catalysts with different Co particle sizes. Kinetic studies were performed to understand the effect of Co particle size on catalytic activity. Size-dependent kinetic parameters were developed using a thermodynamic method, to evaluate the structural sensitivity of the CNT-supported Co catalysts. The size-independent FTS reaction rate constant and size-independent adsorption parameter increased with increasing reac-tion temperature. The Polani parameter also depended on catalyst particle size, because of changes in the catalyst surface coverage.