全文获取类型
收费全文 | 912篇 |
免费 | 8篇 |
国内免费 | 5篇 |
专业分类
化学 | 760篇 |
力学 | 16篇 |
数学 | 87篇 |
物理学 | 62篇 |
出版年
2022年 | 9篇 |
2021年 | 11篇 |
2020年 | 7篇 |
2016年 | 11篇 |
2015年 | 11篇 |
2014年 | 7篇 |
2013年 | 23篇 |
2012年 | 38篇 |
2011年 | 54篇 |
2010年 | 33篇 |
2009年 | 16篇 |
2008年 | 45篇 |
2007年 | 50篇 |
2006年 | 55篇 |
2005年 | 49篇 |
2004年 | 48篇 |
2003年 | 40篇 |
2002年 | 32篇 |
2001年 | 14篇 |
2000年 | 7篇 |
1999年 | 11篇 |
1998年 | 17篇 |
1997年 | 20篇 |
1996年 | 20篇 |
1995年 | 14篇 |
1994年 | 10篇 |
1993年 | 14篇 |
1992年 | 18篇 |
1991年 | 16篇 |
1990年 | 16篇 |
1989年 | 8篇 |
1988年 | 15篇 |
1987年 | 9篇 |
1986年 | 5篇 |
1985年 | 12篇 |
1984年 | 11篇 |
1983年 | 11篇 |
1982年 | 9篇 |
1981年 | 9篇 |
1980年 | 14篇 |
1979年 | 12篇 |
1978年 | 9篇 |
1977年 | 10篇 |
1976年 | 9篇 |
1975年 | 12篇 |
1974年 | 8篇 |
1973年 | 14篇 |
1972年 | 3篇 |
1971年 | 4篇 |
1967年 | 3篇 |
排序方式: 共有925条查询结果,搜索用时 15 毫秒
51.
52.
53.
Electrochemical properties of iron oxides, crystallographic data and examination of etching pits by scanning electron microscopy, suggest that ferric iron has electrochemical reactivity which differs according to its crystallographic position in the solid. 相似文献
54.
Frennet A Visart de Bocarmé T Bastin JM Kruse N 《The journal of physical chemistry. B》2005,109(6):2350-2359
The aim of this paper is to demonstrate the importance of providing time-resolved information in catalysis research. Two truly in situ methods will be presented and compared for their merits and drawbacks: chemical transient kinetics (CTK) and pulsed field desorption mass spectrometry (PFDMS). The presentation will be given by way of example choosing the syngas (CO/H2) reaction over cobalt-based catalysts as a catalytic process. Despite numerous efforts in the past, the mechanism of this reaction is still under debate. In CTK the reaction is studied on a metal-supported catalyst under flow conditions in a pressure range extending from atmospheric pressure down to 100 Pa. Sudden changes in the partial pressures of the reactants then allow following the relaxation to either steady-state conditions ("transients") or cleanoff ("back transients"). In PFDMS short field pulses of several volts per nanometer are applied to a model catalyst which resembles a single metal particle grain (a "tip"). These pulses intervene during the ongoing reaction under flow conditions at pressures ranging from 10(-1) to 10(-5) Pa and cause field desorption of adsorbed species. This method is particularly suited to detect reaction intermediates in a time-dependent manner since the repetition frequency of the pulses can be systematically varied. It is shown that both methods lead to complementary results. While CTK allows conclusions on the mechanism of CO hydrogenation by following the time-dependent formation of hydrocarbon species, PFDMS provides insight into the initial steps leading to adsorbed CxHy species. A quantitative assessment of the CTK data allows the demonstration that the catalyst under working conditions is in an oxidized rather than metallic state. The initial steps to oxidation are also traced by PFDMS. Most importantly, however, CTK results allow formulation of a reaction mechanism that is common for both hydrocarbon and oxygenate formation and is based on the occurrence of a formate-type species as the most abundant surface intermediate. 相似文献
55.
56.
Thieuleux C Quadrelli EA Basset JM Döbler J Sauer J 《Chemical communications (Cambridge, England)》2004,(15):1729-1731
The silica-supported Zr(iv) dihydride [(triple bond)SiO)2ZrH2] reacts quickly and completely with methane to yield [(triple bond)SiO)2ZrMe2] through the intermediate [(triple bond)SiO)2ZrHMe], while its monohydride analogue [(triple bond)SiO)3ZrH] yields the monomethylated product [(triple bond)SiO)3ZrMe] slowly and incompletely. 相似文献
57.
Barboiu M Prodi L Montalti M Zaccheroni N Kyritsakas N Lehn JM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(12):2953-2959
The terpy-derived (terpy=terpyridine) ligand 1 has an extended W shape in which the two appended photoactive pyrenyl groups are held apart. On binding of a zinc(II) ion with a terpy group, ligand 1 is converted into complex 2 whereby it adopts a U shape, thus stacking the aromatic units. This structural modification leads to a very pronounced change in photophysical properties: from a highly fluorescent free ligand to a very weakly emitting complex. The W/U structural switching can be reversibly induced by the addition of a competitive tren ligand, which binds and releases a zinc(II) ion under protonation/deprotonation cycles, thus leading to oscillations in light emission. Therefore, the present system performs periodic modulation of optical output through a nanomechanical shape-flipping motion, triggered by metal ion binding and fuelled by acid-base neutralisation energy. Overall, it represents an ion-triggered opto-mechanical supramolecular device. 相似文献
58.
The oxidation state of the cobalt centres can be controlled by modification of the protonation state in [2 x 2] grid-like arrays based on ionisable bis(hydrazone) ligands, allowing conversion of the paramagnetic Co(II)(4) into the diamagnetic Co(III)(4) grid. 相似文献
59.
Trokiner A Bessière A Thouvenot R Hau D Marko J Nardello V Pierlot C Aubry JM 《Solid state nuclear magnetic resonance》2004,25(4):209-215
In order to get some insight into the mechanism of the disproportionation of hydrogen peroxide catalyzed by calcium hydroxide, 43Ca NMR spectra of enriched samples of calcium peroxides and of their precursors have been studied in both solution and solid state. This study demonstrates that no well-defined peroxidized calcium species are formed in solution, showing that the catalytic role of calcium is likely restricted to the solid state. Most of the calcium compounds that could be involved in the catalytic process have been investigated with solid state NMR. The shift and quadrupolar parameters of Ca(OH)2, CaO2.8H2O and CaO2.2H2O2 are reported for the first time. These parameters are different enough to allow the quantitative analysis of a complex mixture of these compounds by NMR. 相似文献
60.
Herein we describe the catalytic activity of 1, a well-defined Re alkylidene complex supported silica, in the reaction of olefin metathesis. This system is highly active for terminal and internal olefins with initial rates up to 0.7 mol per mol Re per s. It also catalyses the self-metathesis of methyl oleate (MO) without the need of co-catalysts. The turnover numbers can reach up to 900 for MO, which is unprecedented for a heterogeneous Re-based catalyst. Moreover the use of silica as a support can bring major advantages, such as the possibility to use branched olefins like isobutene, which are usually incompatible with alumina-based supports; therefore, the formation of isoamylene from the cross-metathesis of propene and isobutene can be performed. All these results are in sharp contrast to what has been found for other silica- or alumina-supported rhenium oxide systems, which are either completely inactive (silica system) or typically need co-catalysts when functionalised olefins are used. Finally the initiation step corresponds to a cross-metathesis reaction to give a 3:1 mixture of 3,3-dimethylbutene and trans-4,4-dimethylpent-2-ene, and make this catalyst the first generation of well-defined Re-based heterogeneous catalysts. 相似文献