全文获取类型
收费全文 | 2995篇 |
免费 | 548篇 |
国内免费 | 392篇 |
专业分类
化学 | 3181篇 |
晶体学 | 63篇 |
力学 | 4篇 |
综合类 | 23篇 |
数学 | 4篇 |
物理学 | 660篇 |
出版年
2024年 | 6篇 |
2023年 | 45篇 |
2022年 | 82篇 |
2021年 | 115篇 |
2020年 | 152篇 |
2019年 | 145篇 |
2018年 | 98篇 |
2017年 | 115篇 |
2016年 | 195篇 |
2015年 | 180篇 |
2014年 | 187篇 |
2013年 | 321篇 |
2012年 | 220篇 |
2011年 | 161篇 |
2010年 | 150篇 |
2009年 | 158篇 |
2008年 | 153篇 |
2007年 | 160篇 |
2006年 | 165篇 |
2005年 | 172篇 |
2004年 | 124篇 |
2003年 | 117篇 |
2002年 | 129篇 |
2001年 | 56篇 |
2000年 | 63篇 |
1999年 | 39篇 |
1998年 | 75篇 |
1997年 | 70篇 |
1996年 | 59篇 |
1995年 | 43篇 |
1994年 | 25篇 |
1993年 | 23篇 |
1992年 | 26篇 |
1991年 | 24篇 |
1990年 | 13篇 |
1989年 | 13篇 |
1988年 | 12篇 |
1987年 | 8篇 |
1986年 | 4篇 |
1985年 | 3篇 |
1983年 | 1篇 |
1982年 | 3篇 |
1981年 | 2篇 |
1980年 | 7篇 |
1979年 | 3篇 |
1978年 | 3篇 |
1976年 | 2篇 |
1974年 | 2篇 |
1973年 | 3篇 |
1972年 | 2篇 |
排序方式: 共有3935条查询结果,搜索用时 203 毫秒
101.
F. H. B. Lima M. L. Calegaro E. A. Ticianelli 《Russian Journal of Electrochemistry》2006,42(12):1283-1290
This work reviews the studies conducted in this laboratory of the oxygen reduction reaction (ORR) on electrocatalysts formed
by Pt-M/C (M = V, Cr, Co) and Ag-Pt/C alloys and on different Mn oxides (MnO/C, Mn3O4/C, MnO2/C) in KOH electrolyte. The physical and electronic properties of the materials are investigated by in situ XAS (x-ray absorption
spectroscopy) in the XANES (x-ray absorption near edge structure) region. The electrocatalytic activity for the ORR on the
different catalysts is compared through mass-transport-corrected Tafel plots. The XANES results for the Pt-M/C and Ag-Pt/C
composites at high electrode potentials show lower vacancy of the Pt 5d band compared to pure Pt/C, while for the results indicate a chance of the Mn oxidation state as a function of the electrode
potential. The electrochemical measurements evidence increased electrocatalytic activity of the Pt alloys compared to pure
Pt and this is attributed to a lowering of the adsorption strength of adsorbed oxygen species caused by the reduced Pt reactivity.
An activity enhancement of the Ag atoms on the Ag-Pt/C alloys compared to pure Ag is ascribed to an electronic effect induced
by the presence of Pt, increasing the Ag-O adsorption strength. In the case of the MnyOx/C materials, the electrochemical results show low activity for MnO/C and higher activity for MnO2/C and Mn3O4/C. This is explained based on the activation for the ORR, which is higher for the material with higher MnO2 contents and the occurrence of a mediation processes involving the reduction of Mn(IV) to Mn(III), followed by the electron
transfer of Mn(III) to oxygen.
Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 12, pp. 1417–1426.
Based on the report delivered at the 8th International Frumkin Symposium “Kinetics of the Electrode Processes,” October 18–22,
2005, Moscow.
The text was submitted by the authors in English. 相似文献
102.
G. A. Gaddy J. L. McLain E. S. Steigerwalt R. Broughton B. L. Slaten G. Mills 《Journal of Cluster Science》2001,12(3):457-471
Fibers and films prepared from blends of poly(vinyl alcohol) and poly(acrylic acid) were found to be suitable matrices for the solid-state photoreduction of silver ions in the presence of air. Fast generation of nanometer-sized silver crystallites was observed when fibers of polymer blends crosslinked with dimethyl sulfoxide were irradiated with 350nm light. Optical determinations of the formation kinetics were carried out using thin films of noncrosslinked as well as lightly and heavily crosslinked polymer blends. Small Ag clusters were detected initially, which were stable in the dark but transformed into larger metal particles upon further illumination. Both formation processes occurred only under high light intensity illumination and the kinetic data were inconsistent with monophotonic mechanisms. 相似文献
103.
A. V. Safronova L. N. Bochkarev N. E. Stolyarova I. K. Grigorieva I. P. Malysheva G. V. Basova G. K. Fukin E. V. Baranov Yu. A. Kurskii G. A. Abakumov 《Russian Chemical Bulletin》2006,55(2):218-221
New germanium-containing tungsten carbyne complexes Ph3GeC≡W(CH2R)3 (R = But or SiMe3) were synthesized by the reaction of the alkoxy derivative Ph3GeC≡W(OBut)3 with alkyllithium reagents RCH2Li. The new compounds were isolated in individual form as crystals in 95 and 90% yields, respectively, and were characterized
by elemental analysis, 1H and 13C NMR spectroscopy, and X-ray diffraction. X-ray diffraction study showed that the coordination environment of the W and Ge
atoms in the Ph3GeC≡ W(CH2But)3 and Ph3GeC≡W(CH2SiMe3)3 complexes can be described as a distorted tetrahedron.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 213—216, February, 2006. 相似文献
104.
The Negishi cross-coupling reaction of vinylic- and aryltellurides with heteroarylzinc chlorides catalyzed by PdCl2/CuI is described. This cross-coupling reaction is general and permits the formation of a new sp2-sp2 carbon bond in good yields and high stereoselectivity. 相似文献
105.
Assembly of [Ag(CN)2]^- units with M(Ⅱ)-diamine complex cations [Cu(LN-N)2]^2+, where LN-N represents L2-diaminopropane (pn) and ethylenediamine (en), afforded two complexes, [Cu(pn)2][Ag2(CN)4] (1) and [Cu(en)2][Ag3(CN)5] (2), which were characterized by elemental analysis, IR, UV-Vis and ESR spectra. Single crystal X-ray analyses show that these complexes have 2D and 3D architectures through silver-silver interactions and other weak interactions. The luminescence behaviors of the two complexes were also studied by means of emission spectra. 相似文献
106.
Reactivity of Tris(dialkylthiophosphinyl)phosphines – Crystal Structure of [Ag{O[P(S)Me2]2}2][AsF6] In contrast to tris(dialkylphosphoryl)phosphines the reaction of tris(dimethylthiophosphinyl)phosphine with transition metal hexafluoroarsenates of the type [M(SO2)m [AsF6]n (M = Ag, m = 0, n = 1; M = Fe, Cd, m = n = 2) forms no molecular 2 : 1-complexes but polymeric products. The silver polymer is transformed into [Ag{O[P(S)Me2]2}2][AsF6], which is also formed by the reaction of Ag[AsF6] with O[P(S)Me2]2. It crystallizes in the space group P1 with a = 862.5(2), b = 1 241.4(2), c = 1 254.0(3)pm, α = 80.34(1), β = 101.99(6), γ= 73.75(1)° (at 20°C) and Z = 2. The central silver atom is surrounded by four sulphur atoms in a slighly distorted tetrahedron. The average (Ag? S) and (P? S) bond lengthes are 259.4(2) pm and 194.9(2)pm, respectively. 相似文献
107.
A. A. Isaeva A. I. Baranov Th. Doert M. Ruck V. A. Kulbachinskii R. A. Lunin B. A. Popovkin 《Russian Chemical Bulletin》2007,56(9):1694-1700
New metal-rich mixed nickel-silicon and nickel-germanium chalcogenides, Ni5.68SiSe2, Ni5.46GeSe2, and Ni5.42GeTe2, were synthesized by high-temperature ceramic techniques. The X-ray diffraction study of single crystals grown from a molten
flux revealed that the compounds are isostructural and crystallize in the tetragonal system (space group I4/mmm, Z = 2). These compounds are the first members of the family of M7−δEX2-type (M = Ni or Pd; E = Sn or Sb; X is chalcogen) intergrowth structures containing “light” p elements E. Resistivity measurements on pressed textured pellets showed that both selenides are anisotropic metallic conductors
in the directions parallel and perpendicular to the heterometallic bond systems. The geometric criteria of stability of the
intergrowth structure type under consideration are discussed.
Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1632–1638, September, 2007. 相似文献
108.
Michael Chariss Andrea Zickgraf Heike Stenger Elmar Bru Cristelle Desmarquet Martin Drger Silke Gerstmann Dainis Dakternieks James Hook 《Polyhedron》1998,17(25-26)
44 members of thecompound series Ph4−nMRn (M=Si, Ge, Sn, Pb; R=o-, m-, p-Tol; n=0–4) were synthesized (15 newcompounds). The crystal structures of Ph3Sn (o-Tol) and PhSn (o-Tol)3 were determined and compared to 16 known structures. Subject to the distanced (M–C), an interplay between through-space π–π repulsion and π–σ attraction leads to either elongated or compressed tetrahedral geometry. 29 Si-, 119 Sn- and 207 Pb-NMR chemical shifts were determined in solution and in the solid state. 73 Ge chemical shifts were measured only in solution. Anupfield or downfield sagging of the chemical shifts along each series is rationalized in terms of a π–σcharge transfer which is constrained by torsion of the aromatic groups. 相似文献
109.
Bihlmeier A Gonsior M Raabe I Trapp N Krossing I 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(20):5041-5051
The unexpected but facile preparation of the silver salt of the least coordinating [(RO)3Al‐F‐Al(OR)3]? anion (R=C(CF3)3) by reaction of Ag[Al(OR)4] with one equivalent of PCl3 is described. The mechanism of the formation of Ag[(RO)3Al‐F‐Al(OR)3] is explained based on the available experimental data as well as on quantum chemical calculations with the inclusion of entropy and COSMO solvation enthalpies. The crystal structures of (RO)3Al←OC4H8, Cs+[(RO)2(Me)Al‐F‐Al(Me)(OR)2]?, Ag(CH2Cl2)3+[(RO)3Al‐F‐Al(OR)3]? and Ag(η2‐P4)2+[(RO)3Al‐F‐Al(OR)3]? are described. From the collected data it will be shown that the [(RO)3Al‐F‐Al(OR)3]? anion is the least coordinating anion currently known. With respect to the fluoride ion affinity of two parent Lewis acids Al(OR)3 of 685 kJ mol?1, the ligand affinity (441 kJ mol?1), the proton and copper decomposition reactions (?983 and ?297 kJ mol?1) as well as HOMO level and HOMO–LUMO gap and in comparison with [Sb4F21]?, [Sb(OTeF5)6]?, [Al(OR)4]? as well as [B(RF)4]? (RF=CF3 or C6F5) the [(RO)3Al‐F‐Al(OR)3]? anion is among the best weakly coordinating anions (WCAs) according to each value. In contrast to most of the other cited anions, the [(RO)3Al‐F‐Al(OR)3] anion is available by a simple preparation in conventional inorganic laboratories. The least coordinating character of this anion was employed to clarify the question of the ground state geometry of the Ag(η2‐P4)2+ cation (D2h, D2 or D2d?). In agreement with computational data and NMR spectra it could be shown that the rotation along the Ag‐(P‐P‐centroid) vector has no barrier and that the structure adopted in the solid state depends on packing effects which lead to an almost D2h symmetric Ag(η2‐P4)2+ cation (0 to 10.6° torsion) for the more symmetrical [Al(OR)4]? anion, but to a D2 symmetric Ag(η2‐P4)2+ cation with a 44° twist angle of the two AgP2 planes for the less symmetrical [(RO)3Al‐F‐Al(OR)3]? anion. This implies that silver back bonding, suggested by quantum chemical population analyses to be of importance, is only weak. 相似文献
110.
S. Agnello R. Boscaino F. La Mattina S. Grandi A. Magistris 《Journal of Sol-Gel Science and Technology》2006,37(1):63-68
We have studied the generation mechanisms of H(II) paramagnetic centers in Ge-doped silica by investigating up to 104 mol ppm sol-gel Ge-doped silica materials. We have considered materials with the same concentrations of Ge but that are produced
by two different densification routes that give rise to different concentrations of Ge-related oxygen deficient centers (GeODC(II)).
These centers are characterized by an optical absorption band at ∼5.2 eV (B2β band) and two related emissions at ∼3.2 eV and ∼4.3 eV. The GeODC(II) content was estimated by absorption and emission measurements.
The H(II) centers were induced by room temperature γ-ray irradiation and their concentration was determined by electron paramagnetic
resonance measurements.
The comparison between the two kinds of materials, obtained by different preparations, shows that the GeODC(II) concentration
increases with the Ge content and is enhanced by vacuum densification. The comparison of irradiated samples shows that beyond
the already known process of conversion of preexisting GeODC(II) into H(II) centers, another generation process of H(II) centers
is effective that involves irradiation induced GeODC(II). 相似文献