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41.
42.
Self‐assembled molecular aggregates of fluoroalkyl end‐capped N‐(1,1‐dimethyl‐3‐oxobutyl)‐ and N,N‐dimethyl‐acrylamide oligomers in methanol were found to interact with phthalocyanines as guest molecules to exhibit good solubility. On the other hand, the corresponding nonfluorinated oligomers were not effective in solubilizing phthalocyanines under similar conditions. In these oligomers, fluorinated N‐(1,1‐dimethyl‐3‐oxobutyl)acrylamide oligomers were more effective in solubilizing phthalocyanines in methanol. Self‐assemblies formed by fluorinated oligomer‐phthalocyanine complexes are applied to the surface modifications of polystyrene (PS), and the modified PS surface exhibited not only a strong oleophobicity imparted by fluorine but also good hydrophilicity. Thus, these fluorinated molecular aggregate‐phthalocyanine systems are suggested to have high potential for new fluorinated functional materials through their excellent properties imparted by fluorine and phthalocyanines. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 521–525, 2004 相似文献
43.
The first report on heterogeneously catalyzed oxidative cyanation of various tertiary amines to the corresponding α‐amino nitriles with high yields and selectivity by using hydrogen peroxide oxidant in presence of sodium cyanide and Fe(II) phthalocyanine supported on a polymer as catalyst is described. The present method has the added benefits of facile recovery of the catalyst from the reaction mixture and its subsequent use without further activation. Consistent catalytic activity with no metal leaching was observed during this course. 相似文献
44.
Cristhian Berríos Jos F. Marco Claudio Gutirrez María Soledad Ureta-Zaartu 《Electrochimica acta》2009,54(26):6417-6425
The effect of the ligand macrocycle (phenylporphyrin (PP) or phthalocyanine (Pc)) and of the ligand substituent (NH2 or SO3−) on the catalytic activity for the electro-oxidation in a pH 11 buffer electrolyte of 2- and 4-chlorophenol (2-CP and 4-CP), 2,4- and 2,6-dichlorophenol (2,4-DCP and 2,6-DCP), 2,4,6-trichlorophenol (2,4,6-TCP), and pentachlorophenol (PCP) at glassy carbon electrodes modified with electropolymerized Ni(II) macrocycles was studied. The polyphenolic residue deposited at the electrode surface was characterized by cyclic voltammetry, impedance measurements, ex situ Fourier transform infrared spectroscopy (FT-IR) and X-ray Photoelectron Spectroscopy (XPS). A band of aliphatic CO stretching in the IR spectrum of the fouling film produced by potential cycling in 2,4,6-TCP indicated that the aromatic ring had been broken, yielding ketones, aldehydes and/or carboxylic acids. The sulphonated Ni(II) polymers, which showed the Ni(III)/Ni(II) process in the CV, had XP spectra typical of paramagnetic Ni(II), indicating that they contained Ni(OH)2 clusters. On the contrary, the CVs of the amino Ni(II) did not show the Ni(III)/Ni(II) process at all, this process appearing only after previous activation by potential cycling, and only to a small extent. As was to be expected, the XP spectra of activated amino films corresponded to diamagnetic Ni(II), showing that the concentration of Ni(OH)2 clusters was very small. The amino films were less active than the sulpho films for the oxidation of chlorophenols, in agreement with the lower concentration of Ni(OH)2 clusters in the former films. For all electrodes the highest activity was observed for 2,4,6-TCP, since its oxidation yields a phenolic residue which is much more porous than those produced by the other CPs. 相似文献
45.
The interfaces formed between metal phthalocyanines (NiPc and CoPc) and ITO were studied by X-ray and Ultra-Violet Photoelectron Spectroscopies (XPS and UPS, respectively). The results showed the formation of an interfacial dipole in both cases (NiPc/ITO, CoPc/ITO) in different direction due to the different electronic properties of the organic materials. This was evidenced by the shift of the XPS organic related peaks as well as the change of the vacuum level position. A broadening of the HOMO feature at the early steps of deposition, compared to the bulk organic layers, was also observed. The HOMOcut-off position for the NiPc overlayer was found to be at 1.00 ± 0.05 eV of binding energy from the Fermi level of the energy analyser and at 0.80 ± 0.05 eV for the CoPc layer, respectively. A comparison between ITO and polycrystalline Au foil as substrates in interfaces with MePcs (NiPc, CoPc) is also discussed. 相似文献
46.
KonstantinV. Luzyanin Vadim Yu. Kukushkin Maximilian N. Kopylovich Alexey A. Nazarov Markus Galanski Armando J.L. Pombeiro 《Advanced Synthesis \u0026amp; Catalysis》2008,350(1):135-142
Refluxing a mixture of phthalonitrile C6R1R2R3R4(CN)2 1 (R1–R4=H), or its substituted derivatives 2 (R1, R3, R4=H, R2=Me), or 3 (R1, R4=H, R2, R3=Cl) (1 equiv.) and N,N‐diethylhydroxylamine, Et2NOH, (4 equivs.) in methanol for 4 h results ( Route A ) in precipitation of the symmetrical ( 6 and 8 ) and an isomeric mixture of unsymmetrical ( 7 ) phthalocyanines, isolated in good (55–65 %) yields. The reaction of phthalonitriles 1 , 2 , or 4 (R1, R3, R4=H, R2=NO2) (4 equivs.) with Et2NOH (8 equivs.) in the presence of a metal salt MCl2 (M=Zn, Cd, Co, Ni) (1 equiv.) in n‐BuOH or without solvent results in the formation of metallated phthalocyanine species ( 9 – 17 ). Upon refluxing in freshly distilled dry chloroform, phthalonitrile 1 or its substituted analogues 2 , 3 or 5 (R1–R4=F) (1 equiv.) react with N,N‐diethylhydroxylamine (2 equivs.) affording 3‐iminoisoindolin‐1‐ones 18 – 21 ( Route B ) isolated in good yields (55–80 %). All the prepared compounds were characterized with C, H, and N elemental analyses, ESI‐MS, IR, and compounds 18 – 21 also by 1D (1H, 13C{1H}), and 2D (1H,15N‐HMBC and 1H,13C‐HMQC, 1H,13C‐HMBC) NMR spectroscopy. 相似文献
47.
48.
Zhihai Cheng Shixuan Du Wei Guo Li Gao Zhitao Deng Nan Jiang Haiming Guo Hao Tang H. -J. Gao 《Nano Research》2011,4(6):523-530
High-resolution scanning tunneling microscope images of iron phthalocyanine and zinc phthalocyanine molecules on Au(111) have
been obtained using a functionalized tip of a scanning tunneling microscope (STM), and show rich intramolecular features that
are not observed using clean tips. Ab initio density functional theory calculations and extended Hückel theory calculations revealed that the imaging of detailed electronic
states is due specifically to the decoration of the STM tip with O2. The detailed structures are differentiated only when interacting with the highly directional orbitals of the oxygen molecules
adsorbed on a truncated, [111]-oriented tungsten tip. Our results indicate a method for increasing the resolution in generic
scans and thus, have potential applications in fundamental research based on high-resolution electronic states of molecules
on metals, concerning, for example, chemical reactions, and catalysis mechanisms. 相似文献
49.
Glassy carbon electrodes modified by electropolymerization of two water-soluble compounds, Ni(II)tetrasulphophthalocyanine (NiTSPc) and Ni(II)tetrasulphophenylporphyrin (NiTSPP), and of two water-insoluble compounds, Ni(II)tetraaminophthalocyanine (NiTAPc) and Ni(II)tetraaminophenylporphyrin (NiTAPP), have been studied by impedance measurements. While in the tetrasulpho films the Ni(II)/Ni(III) process was operative, the tetraamino films required activation by repetitive potential cycling before the peaks of this process appeared in the CV, and even then the charge was a fraction of that shown by the tetrasulpho films. The Nyquist plots of all these films shown in the potential range of the Ni(II)/Ni(III) process the semicircle typical of a charge transfer, the charge-transfer resistance decreasing very much with increasing potential. The uncompensated resistance of the GC electrode was barely affected by the films, showing that they were very porous. The impedance at low frequencies of the thick polyNiTSPP film, the thin polyNiTSPc film, and also the activated polyNiTAPc film fitted the Warburg model, the diffusing species being probably the hydroxyl ions involved in the process. 相似文献
50.
A new tetrakis 4‐(2,5‐di‐2‐thiophen‐2‐yl‐pyrrol‐1‐yl) substituted nickel phthalocyanine (NiPc‐SNS) was synthesized and characterized by elemental analysis, Fourier Transform Infrared (FT‐IR), and UV–vis spectroscopies. The electrochemical polymerization of this newly synthesized NiPc‐SNS was performed in dichloromethane (DCM)/tetrabutylammonium perchlorate (TBAP) solvent/electrolyte couple. An insoluble film was deposited on the electrode surface, both during repetitive cycling and constant potential electrolysis at 0.85 V. Resulting polymer film, P(NiPc‐SNS), was characterized utilizing UV–vis and FT‐IR spectroscopic techniques and its electrochemical behavior was investigated via cyclic voltammetry (CV). Spectroelectrochemical behavior of the polymer film on indium tin oxide (ITO) working electrode was investigated by recording the electronic absorption spectra, in situ, in monomer‐free electrolytic solution at different potentials and it is found that the P(NiPc‐SNS) film can be reversibly cycled between 0.0 and 1.1 V and exhibits electrochromic behavior; dark olive green in the neutral and dark blue in the oxidized states with a switching time of 1.98 s. Furthermore, the band gap of P(NiPc‐SNS) was calculated as 2.27 eV from the onset of π–π* transition of the conjugated backbone. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011 相似文献