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11.
All-electron full-potential linearized augmented plane-wave calculations of the surface energy, work function, and interlayer spacings of close-packed metal surfaces are presented, in particular, for the free-electron-like metal surfaces, Mg(0 0 0 1) and Al(1 1 1), and for the transition metal surfaces, Ti(0 0 0 1), Cu(1 1 1), Pd(1 1 1), and Pt(1 1 1). We investigate the convergence of the surface energy as a function of the number of layers in the slab, using the Cu(1 1 1) surface as an example. The results show that the surface energy, as obtained using total energies of the slab and bulk from separate calculations, converges well with respect to the number of layers in the slab. Obviously, it is necessary that bulk and surface calculations are performed with the same high accuracy. Furthermore, we discuss the performance of the local-density and generalized gradient approximations for the exchange-correlation functional in describing the various surface properties. 相似文献
12.
Ganapati V. Shanbhag 《Tetrahedron letters》2006,47(2):141-143
Heterogeneous intermolecular hydroamination of alkynes with aromatic amines using inexpensive transition metal-exchanged clay catalysts was investigated. Reaction of terminal alkynes with aromatic amines gave higher yields of imines. 相似文献
13.
meso-四(4-乙酰氧基苯)卟啉-铜(Ⅱ)-乳化剂OP体系荧光熄灭法测定微量铜(Ⅱ)的研究 总被引:1,自引:0,他引:1
本文研究了高灵敏的meso-四(4-乙酰氧基苯)卟啉[T(4-AOP)P]-铜(Ⅱ-乳化剂OP体系。在酸度为pH5.0~5.6范围内形成的三元络合物可引起T(4-AOP)P-OP荧光强度的定量熄灭,其Ex=413nm,EM=656.9nm,Cu(Ⅱ)浓度在0~0.150μg/ml范围内有良好的线性关系,回归方程F=25.51-8.45m,试验了14种离子的干扰影响,并用此法测定了小球藻中Cu的含量,回收率达96~104%。 相似文献
14.
Hatsuo Yamamura Kousuke Satake Rieko Hirasawa Shinichi Yamada Masao Kawai 《Journal of inclusion phenomena and macrocyclic chemistry》2007,57(1-4):261-264
A novel cyclodextrin (CD) dimer linked with a bis(picolinyl)cystine (Cys) moiety was prepared by the coupling of Boc-protected
Cys with amino-modified CDs, followed by deprotection of the Boc groups and bispicolinylation. The dimer showed less affinity
to an organic guest molecule compared to that of a native CD monomer. It was attributed to an intramolecular inclusion of
the pyridine moiety into CD cavity. The dimer caused significant increase of its organic guest affinity by an addition of
a copper ion. The included pyridine group may come out of a CD cavity to bind the copper ion and the two CDs included cooperatively
and intermolecularly a guest molecule with high affinity. 相似文献
15.
István Szilágyi László. Horváth Imre Labádi Klara Hernadi István Pálinkó Tamás Kiss 《Central European Journal of Chemistry》2006,4(1):118-134
An imidazolate-bridged copper(II)-zinc(II) complex (Cu(II)-diethylenetriamino-μ-imidazolato-Zn(II)-tris(2-aminoethyl)amine perchlorate (denoted as “Cu,Zn complex”) and a simple copper(II) complex (Cu(II)-tris(2-aminoethyl)
amine chloride (“Cu-tren”) were prepared and immobilised on silica gel (by hydrogen or covalent bonds) and montmorillonite
(by ion exchange). The immobilised substances were characterised by FT-IR spectroscopy and their thermal characteristics were
also studied. The obtained materials were tested in two probe reactions: catalytic oxidation of 3,5-di-tert-butyl catechol (DTBC) (catecholase activity) and the decomposition of hydrogen peroxide (catalase activity). It was found
that the catecholase activity of the Cu,Zn complex increased considerably upon immobilization on silica gel via hydrogen bonds and intercalation by ion exchange among the layers of montmorillonite. The imidazolate-bridged copper(II)-zinc(II)
complex and its immobilised versions were inactive in hydrogen peroxide decomposition. The Cu(II)-tris(2-aminoethyl)amine
chloride complex displayed good catalase activity; however, immobilisation could not improve it. 相似文献
16.
本文研究了鸟瞟呤(Gua)和次黄嘌呤(Hxa)铜络合物在悬汞电极(HMDE)上的吸附作用和电极反应机理,溶液中形成的1:1络合物有强烈吸附性,通过分子结构的比较,推断出Cu~(2+)与Gua和Hxa的咪唑环N(7)和外环氧O(6)原子结合形成封闭的五元环。嘌呤环的π-电子有使分子呈平面吸附的趋势,但是Gua络合物分子优先取“倾斜”定向;随着表面吸附浓度增加,Hxa络合物分子存在从“平面”向“垂直”的再定向作用。本文测定了单层吸附浓度、包含的电量和每个分子占据的面积。络合物吸附得到S形等温线,它与Frumkin吸附等温线接近。本文还列出有关吸附参数B、a、△G_A~O和θ~*的计算结果。 相似文献
17.
Gui-Chang Wang Ling Jiang Yoshitada Morikawa Junji Nakamura Zun-Sheng Cai Yin-Ming Pan Xue-Zhuang Zhao 《Surface science》2004,570(3):205-217
The adsorption behavior and thermal activation of carbon dioxide on the Cu(1 1 1), Cu(1 0 0), and Cu(1 1 0) surfaces have been investigated by means of density functional theory calculations and cluster models and periodic slabs. According to the cluster models, the optimized results indicate that the basis set of C and O atoms has a distinct effect on the adsorption energy, but an indistinct one on the equilibrium geometry. For the CO2/Cu(hkl) adsorption systems studied here, the final structure of adsorbed CO2 is near linear and the preferred modes for the adsorption of CO2 onto the Cu(1 1 1), Cu(1 0 0), and Cu(1 1 0) surfaces are the side-on adsorption at the cross bridge site with an adsorption energy of 13.06 kJ/mol, the side-on adsorption at the short bridge site (13.54 kJ/mol), and the end-on adsorption on the on-top site with C–O bonds located along the short bridge site (26.01 kJ/mol), respectively. However, the calculated adsorption energies from periodic slabs are lower as compared to the experimental data as well as the cluster model data, indicating that the periodic slab approach of generalized gradient approximation in the density function theory may be not suitable to obtain quantitative information on the interaction of CO2 with Cu(hkl) surfaces. 相似文献
18.
The adsorption of CN on Cu(1 1 1), Ni(1 1 1) and Ni(1 0 0) has been investigated using density functional theory (DFT). While experimental studies of CN on Cu(1 1 1) show the molecular axis to be essentially parallel to the surface, the normally-preferred DFT approach using the generalised gradient approximation (GGA) yields a lowest energy configuration with the C-N axis perpendicular to the surface, although calculations using the local density approximation (LDA) do indicate that the experimental geometry is energetically favoured. The same conclusions are found for CN on Ni(1 1 1); on both surfaces bonding through the N atom is always unfavourable, in contrast to some earlier published results of ab initio calculations for Ni(1 1 1)/CN and Ni(1 0 0)/CN. The different predictions of the GGA and LDA approaches may lie in subtly different relative energies of the CN 5σ and 1π orbitals, a situation somewhat similar to that for CO adsorbed on Pt(1 1 1) which has proved challenging for DFT calculations. On Ni(1 0 0) GGA calculations favour a lying-down species in a hollow site in a geometry rather similar to that found experimentally and in GGA calculations for CN on Ni(1 1 0). 相似文献
19.
Nanocrystalline thin films of copper selenide have been grown on glass and tin doped-indium oxide substrates using chemical method. At ambient temperature, golden films have been synthesized and annealed at 200 °C for 1 h and were examined for their structural, surface morphological and optical properties by means of X-ray diffraction (XRD), scanning electron microscopy and UV-vis spectrophotometry techniques, respectively. Cu2−xSe phase was confirmed by XRD pattern and spherical grains of 30 ± 4 - 40 ± 4 nm in size aggregated over about 130 ± 10 nm islands were seen by SEM images. Effect of annealing on crystallinity improvement, band edge shift and photoelectrochemical performance (under 80 mW/cm2 light intensity and in lithium iodide electrolyte) has been studied and reported. Observed p-type electrical conductivity in copper selenide thin films make it a suitable candidate for heterojunction solar cells. 相似文献
20.
Gurkan Hizal Umit Tunca Sermin Aras Humeyra Mert 《Journal of polymer science. Part A, Polymer chemistry》2006,44(1):77-87
Copper‐catalyzed controlled/living radical polymerization (LRP) of styrene (St) was conducted using the silica gel‐supported CuCl2/N,N,N′,N′,N″‐pentamethyldiethylenetriamine (SG‐CuCl2/PMDETA) complex as catalyst at 110 °C in the presence of a definite amount of air. This novel approach is based on in situ generation and regeneration of Cu(I) via electron transfer reaction between phenols and Cu(II). Sodium phenoxide or p‐methoxyphenol was used as a reducing agent of Cu(II) complexes in LRP. The number–average molecular weight, Mn,GPC, increases linearly with monomer conversion and agrees well with the theoretical values up to 85% conversion The molecular weight distribution, Mw/Mn, decreases as the conversion increases and reaches values below 1.2. The catalyst was recovered in aerobic condition and reused in copper‐catalyzed LRP of St. For the second run, the number–average molecular weights increased with monomer conversion and the polydispersities decreased as the polymerization proceeded and reached to the value <1.3 at 81% conversion. The recycled catalyst retained 90% of its original activity in the subsequent polymerization. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 77–87, 2006 相似文献