Synthesis, photoluminescence, and theoretical studies of novel Cu(I) complex

A novel diimine Cu(I)complex [Cu(ABPQ)(DPEphos)]BF4 [ABPQ and DPEphos are acenaphtho[1,2-b]bipyrido[2,3-h:3,2-f]quinoxaline and bis(2-(diphenylphosphanyl)phenyl) ether, respectively] is synthesized, and its photophysical properties are experimentally and theoretically characterized. The emission bands centered at ca. 400/470 and 550 nm of [Cu(ABPQ)(DPEphos)]BF4 are attributed to the ligand-centered pi -> pi* transition and the metal-to-ligand charge transfer d pi(Cu) -> pi*(N-N) transition, respectively. The luminescence quantum yield of [Cu(ABPQ)(DPEphos)]BF4 in CHCl3 is found to be about five times higher than that of [Cu(Phen)(DPEphos)]BF4.

Synthesis and Crystal Structure of a New 3D Copper B-Paradodecatungstate Compound: [Na-2(H2O)(8)][Na-8(H2O)(20)][Cu(en)(2)][W12O42] center dot 3H(2)O

A new polyoxotungstate complex [Na-2(H2O)(8)][Na-8(H2O)(20)][Cu(en)(2)][W12O42] center dot 3 H2O (1) (en = ethylenediamine) has been synthesized in aqueous solution and characterized by elemental analysis, IR spectroscopy and TG analysis, together with a single crystal X-ray diffraction study. In compound 1, the Cu(en)(2)(2+) complex cation links the [W12O42](12-) anions to form a I D chain, and the ID chains are further interconnected with Na-8(H2O)(20)(8+) and Na-2(H2O)(8)(2+) cations to construct a new 3D framework.

Theoretical studies on the reaction mechanism of oxidation of primary alcohols by Zn/Cu(II)-phenoxyl radical catalyst

The catalytic mechanism for the oxidation of primary alcohols catalyzed by the two functional models of galactose oxidase (GOase), M-II L (M = Cu, Zn; L = N,N'-bis(3,5-di-tert-butyl-2-hydroxyphenyl)1-2-diiminoquinone)), has been studied by use of the density functional method B3LYP The catalytic cycle of Cu- and Zn-catalysts consists of two parts, namely, substrate oxidation (primary alcohol oxidation) and O-2 reduction (catalyst regeneration). The catalytic mechanisms have been studied for the two reaction pathways (route 1 and route 2). The calculations indicate that the hydrogen atom transfer within the substrate oxidation part is the rate-determining step for both catalysts, in agreement with the experimental observation.

微悬臂梁检测三肽Gly-Gly-His与Cu~(2+)的相互作用过程

将三肽Gly-Gly-His(GGH)共价键合到MPA修饰的微悬臂梁表面,研究了肽与Cu2+的相互作用过程。研究发现,在Cu2+浓度较高时,Cu2+能快速与不同肽链上的羧基和咪唑环配位,并通过连锁反应诱导悬臂梁向镀金面偏转;而后肽链上的氮原子与Cu2+配位,同时构象发生变化,由直链转变成折叠状,进而增加链间的作用力使悬臂梁反向偏转;而Cu2+浓度低时不能实现连锁反应诱导悬臂梁表面快速的形成向内的拉力,直接通过构象变化推动悬臂梁反向偏转。考察了溶液pH值、Cl-浓度对GGH与Cu2+作用的影响,结果表明,在pH7.0的条件下GGH与Cu2+作用导致悬臂梁偏转最大。Cl-的存在会与Cu2+形成CuCl2x?x配合物不易与肽链结合。

CO_2在TiO_2-CuO修饰Cu电极上的光电化学还原

制备了TiO2-CuO修饰Cu电极,并对CO2在该复合光电电极上的还原行为进行了研究。光电化学测试表明,TiO2有助于电极的光电转换,能注入更多的电子促进CO2还原。TiO2-CuO/Cu复合电极在光照条件下对CO2具有很好的光电催化还原活性,使还原电位正移约100 mV,同时有效地抑制了水的光电分解。Mott-Schottky曲线测定表明,TiO2-CuO/Cu复合电极具有n型半导体性质,其平带电位随光照时间的增加而负移。光谱及色质谱测试证明,CO2在TiO2-CuO/Cu复合电极上的光电化学还原产物为甲酸和甲醛,还有少量乙烯和甲烷。在-1.2 V条件下光照3 h,CO2的转化率可达32%。基于实验结果对CO2光电还原机理进行了推断。

Interaction of H-2 with transition metal homonuclear dimers Cu-2, Ag-2, Au-2 and heteronuclear dimers PdCu, PdAg and PdAu

The reaction mechanisms of the H-2 with the homonuclear dimers M-2 (Cu, Ag, Au) and the heteronuclear dimers PdM (M = Cu, Ag, Au) were studied by use of density functional theory. For the H-2 reactions with homonuclear dimers M-2 (Cu, Ag, Au), it was found that it is easier for Au-2 to dissociate the hydrogen molecule compared with Cu-2 and Ag-2. For H-2 reactions with the heteronuclear dimers PdM (M = Cu, Ag, An), the hydrogen molecule can be easily dissociated at Pd site, rather than at noble metal site.

Crystallographic and electrochemical characteristics of melt-spun Ti-Zr-Ni-Cu alloys

Ti44Zr32Ni22Cu2 and Ti41Zr29Ni28Cu2 alloys were prepared by the melt-spinning method. The phase structure was analyzed by X-ray diffraction, and the electrochemical performances of the melt-spun alloys were investigated. The results indicated that the Ti44Zr32Ni22Cu2 alloy was composed of the icosahedral quasicrystals and amorphous phases, and the Ti41Zr29Ni28Cu2 alloy comprised icosahedral quasicrystals, amorphous, and Laves phases. The maximum discharge capacity was 141 mAh/g for the Ti44Zr32Ni22Cu2 alloy and 181 mAh/g for the Ti41Zr29Ni28Cu2 alloy, respectively. The Ti41Zr29Ni28Cu2 alloy also showed a better high-rate dischargeabifity and cycling stability. The better electrochemical properties should be ascribed to the high content of Ni, which was beneficial to the electrochemical kinetic properties and made the alloy more resistant to oxidation, as well as to the Laves phase in the Ti41Zr29Ni28Cu2 alloy, which could work as the electro-catalyst and the micro-current collector.

Fast and facile preparation of superhigh aspect-ratio Cu-thiourea nanowires in large quantity

Superhigh aspect-ratio Cu-thiourea (Cu(tu)) nanowires have been synthesized in large quantity via a fast and facile method. Nanowires of Cu (tu)Cl center dot 0.5H(2)O and Cu(tu)Br center dot 0.5H(2)O were found to be 60-100 nm and 100-200 nm, in diameter, and could extend to several millimeters in length. It is found to be the most convenient and facile approach to the fabrication of one-dimensional superhigh aspect-ratio nanomaterials in large scale so far.

Self-assembly of a water chain with tetrameric and decameric clusters in the channel of a mixed-valence (CuCuII)-Cu-I complex

The reaction of Cu(BF4)(2) with pyridine-2,6-dicarboxylic acid (H(2)pydc) and trans-1,2-bis(4-pyridyl)ethylene (bpe) under hydrothermal conditions afforded a porous mixed-valence (CuCuII)-Cu-I coordination polymer. Coexistence of tetrameric and decameric water clusters within the channels of the complex leads to a novel water chain. The metal-organic framework provides both hydrophilic and hydrophobic environments for stabilizing the clusters and retains its integrity upon dehydration and rehydration.

Cu掺杂的NiO的制备及其超级电容器性能

采用低热固相反应法合成掺杂Cu的Ni(OH)2,将其在300℃下热处理得到相应的NiO.电化学测试表明∶掺杂量为n(Ni)∶n(Cu)=100∶0.25时,NiO电极的比容量最高,为99-120 F/g,具有良好的充放电性能,而不掺杂的只有83-111 F/g,因此掺杂Cu有利于提高NiO的电化学性能.

Novel heteroleptic Cu-I complexes with tunable emission color for efficient phosphorescent light-emitting diodes

A series of orange-red to red phosphorescent heteroleptic Cu-I complexes (the first ligand: 2,2 '-biquinoline (bq), 4,4 '-diphenyl2,2 '-biquinoline (dpbq) or 3,3 '-methylen-4,4 '-diphenyl-2,2 '-biquinoline (mdpbq); the second ligand: triphenylphosphine or bis[2-(diphenylphosphino)phenyl]ether (DPEphos)) have been synthesized and fully characterized. With highly rigid bulky biquinoline-type ligands, complexes [Cu(mdpbq)(PPh3)(2)](BF4) and [Cu(mdpbq)(DPEphos)](BF4) emit efficiently in 20 wt % PMMA films with photoluminescence quantum yield of 0.56 and 0.43 and emission maximum of 606 nm and 617 nm, respectively. By doping these complexes in poly(vinyl carbazole) (PVK) or N-(4-(carbazol-9-yl)phenyl)-3,6-bis(carbazol-9-yl) carbazole (TCCz), phosphorescent organic light-emitting diodes (OLEDs) were fabricated with various device structures. The complex [Cu(mdpbq)(DPEphos)](BF4) exhibits the best device performance. With the device structure of ITO/PEDOT/ TCCz:[Cu(mdpbq)(DPEphos)](BF4) (15 wt %)/TPBI/LiF/Al (III), a current efficiency up to 6.4 cd A(-1) with the Commission Internationale de L'Eclairage (CIE) coordinates of (0.61, 0.39) has been realized. To our best knowledge, this is the first report of efficient mononuclear Cu complexes with red emission.

贵金属改性的Cu/ZrO2基合成甲醇催化剂及其制备方法和应用

一种贵金属改性的Ｃｕ／ＺｒＯ↓［２］基合成甲醇催化剂重量组成为Ｃｕ：９－２４％，Ｚｒ７５－９０％，Ｐｄ或Ａｇ０．１－１．０％。用硝酸铜和氧氯化锆的混合溶液，在６０－９０℃下与碳酸钠溶液搅拌状态共沉淀，保持ｐＨ值在９－１１，沉淀经蒸馏水洗涤至无氯离子检出为止，经干燥后在３５０－５５０℃下焙烧，自然冷却至室温后，压片成型，破筛至４０－６０目。用浸渍法引入钯或银助剂，以硝酸盐的形式加入，浸渍时间为１２－２４小时，经红外灯照射烘干后制得催化剂。本发明具有催化剂机械强度好，性能重复性好，制备方法简单，易于操作的优点。