全文获取类型
收费全文 | 7403篇 |
免费 | 981篇 |
国内免费 | 2063篇 |
专业分类
化学 | 9512篇 |
晶体学 | 33篇 |
力学 | 52篇 |
综合类 | 59篇 |
数学 | 7篇 |
物理学 | 784篇 |
出版年
2024年 | 14篇 |
2023年 | 120篇 |
2022年 | 218篇 |
2021年 | 330篇 |
2020年 | 413篇 |
2019年 | 315篇 |
2018年 | 298篇 |
2017年 | 275篇 |
2016年 | 382篇 |
2015年 | 380篇 |
2014年 | 475篇 |
2013年 | 785篇 |
2012年 | 517篇 |
2011年 | 482篇 |
2010年 | 427篇 |
2009年 | 424篇 |
2008年 | 506篇 |
2007年 | 526篇 |
2006年 | 448篇 |
2005年 | 394篇 |
2004年 | 389篇 |
2003年 | 431篇 |
2002年 | 355篇 |
2001年 | 227篇 |
2000年 | 212篇 |
1999年 | 174篇 |
1998年 | 137篇 |
1997年 | 145篇 |
1996年 | 136篇 |
1995年 | 116篇 |
1994年 | 89篇 |
1993年 | 70篇 |
1992年 | 69篇 |
1991年 | 40篇 |
1990年 | 39篇 |
1989年 | 24篇 |
1988年 | 19篇 |
1987年 | 9篇 |
1986年 | 7篇 |
1985年 | 11篇 |
1984年 | 5篇 |
1983年 | 3篇 |
1982年 | 2篇 |
1981年 | 3篇 |
1980年 | 2篇 |
1977年 | 1篇 |
1973年 | 1篇 |
1969年 | 1篇 |
1959年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 578 毫秒
21.
S. V. Semikolenov K. A. Dubkov E. V. Starokon' D. E. Babushkin G. I. Panov 《Russian Chemical Bulletin》2005,54(4):948-956
The kinetics and mechanism of noncatalytic liquid-phase oxidation of but-1-ene and but-2-ene with nitrous oxide in a benzene
solution in the temperature range from 180 to 240°C were studied. Oxidation proceeds via the 1,3-dipolar cycloaddition mechanism to form carbonyl compounds. Both of these reactions occur with close rates and activation
energies and have the first orders with respect to the alkene and N2O. A considerable fraction (39%) of but-1-ene involved in oxidation undergoes cleavage at the double bond yielding propanal
and an equivalent amount of methylene, the latter producing ethylcyclopropane and cycloheptatriene. The oxidation of but-2-ene
proceeds with a minimum bond cleavage and affords methyl ethyl ketone with 84% selectivity. Regularities of the oxidation
of terminal and internal alkenes C2—C8 with nitrous oxide were analyzed using the previously published data.
__________
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 925–933, April, 2005. 相似文献
22.
Shen-shui Lü 《高分子科学》2006,(5):441-447
Two kinds of water-soluble metallophthalocyanines, binuclear cobalt phthalocyanine (Co2Pc2) and binuclear ferric phthalocyanine (Fe2Pc2), were synthesized through phenylanhydride-urea route and characterized by elemental analysis and FT-IR spectra. Binuclear metallophthalocyanine derivatives (Mt2Pc2) were immobilized on silk fibers and modified viscose fibers to construct bioactive fibers of mimic enzyme. Mt2Pc2 was used as the active center of bioactive fibers, viscose and silk fibers as the microenvironments. The catalytic oxidation ability of bioactive fibers on the malodors of methanthiol and hydrogen sulfide was investigated at room temperature. The experimental results indicated that the catalytic activity of such bioactive fibers was closely correlative to the types ofbioactive fibers and substrates. 相似文献
23.
《Magnetic resonance in chemistry : MRC》2003,41(1):37-41
The oxidation of symmetrical disulfides [D ,L ‐cystine ( 1 ) and 3,3′‐dithiobis(propionic acid) ( 2 )] with hydrogen peroxide in D2O–NaOH solution (pH 10–11) was studied by NMR spectroscopy. Assignments of the proton and carbon NMR signals of starting materials ( 1 and 2 ) and products of oxidation are based on conventional 1D NMR methods (DEPT, selective spin decoupling). Formation of C—S bond cleavage products or, in case of 2 , partially oxidized intermediates was not detected. The accelerating effect of Cu2+ cations, but not Fe3+ cations, on the oxidation rate of 1 in basic medium was demonstrated. Copyright © 2002 John Wiley & Sons, Ltd. 相似文献
24.
Recent developments in the aerobic oxidation of alcohols 总被引:1,自引:0,他引:1
25.
Some nickel, copper, and silver salts or complexes are efficient catalysts for the oxidation of benzylic ethers with oxygen in 1,2-dimethoxyethane. Salts of the weakly coordinating anion trifluoroacetate are particularly efficient, approaching (and, in some cases, improving) the yields obtained with cobalt(II) chloride, the best catalyst so far reported. 相似文献
26.
The 2D Rancieite type manganic acid was prepared by reduction of KMnO4 in acidic medium. Its ion exchange behavior allows to prepare alkali derivatives. All compounds were characterized with use of a combination of X-ray diffraction, chemical analyses, TGA, magnetic measurements and spectroscopic techniques. The evolution of their chemical composition versus temperature was studied between 180 and 400 °C. It shows that the dehydration process is partly reversible in these compounds whereas the weak reduction is irreversible. The 2D Rancieite-type manganic acid is readily different from a Birnessite-type phyllomanganate, as shown by several features: the interlayer distance, the ion exchange capacity, the thermal behavior, the interlayer cation content, the manganese average oxidation state, the magnetic behavior and the IR spectrum. 相似文献
27.
The electrochemical oxidation of 1, 3-benzenedithiol was investigated in a 0. 100 mol/L tetrabutylammonium perchlorate/acetonitrile electrolyte. The electrochemical techniques used were potential sweep, bulk electrolysis, rotating disc and the potential step method. The combination of the techniques yielded the number of electrons transferred per molecule, the reaction order, the transfer coefficient, the diffusion coefficient and concentration of dithiol anions, the standard heterogeneous rate constant as well as the formal potential and equilibrium constant of the preceeding dissociation reaction. This paper also illustrates the methods for studying the electrode kinetics of reactions which (a) involve a chemical reaction preceeding the electron-transfer process, (b) have insoluble polymer products, and (c) are totally irreversible. 相似文献
28.
Jiaqiang Wang Hua Fang Ying Li Junjie Li Zhiying Yan 《Journal of molecular catalysis. A, Chemical》2006,250(1-2):75-79
Cobalt-doped mesoporous titania with a crystalline framework synthesized by surfactant templating method presented highly selective (99%) and reasonable conversion rate (49%) of catalytic oxidation of para-chlorotoluene to para-chlorobenzaldehyde in acetic acid using aqueous hydrogen peroxide as oxidant for the first time. Recycling of the catalyst indicates that the catalyst can be used a number of times without losing its activity to a greater extent. By contrast, cobalt-doped mesoporous titania without a crystalline structure and cobalt doped the commercial titania, Degussa P25 prepared by impregnation method with the similar concentration of cobalt were found inactive. The effects of catalyst concentration, reaction time, reaction temperature, and solvents on the performance of the catalyst were also investigated. 相似文献
29.
The enthalpies of formation of simple nonmetal or metalloid oxyanions in aqueous solution are discussed. Archival values are cited and estimates are made. Trends prove evasive. 相似文献
30.
Huayang Zhu Robert J. Kee Jeffrey R. Engel David T. Wickham 《Proceedings of the Combustion Institute》2007,31(2):1965-1972
This paper reports the results of experimental and modeling efforts to characterize partial oxidation of methane to produce synthesis gas (H2 and CO) using metal-substituted hexaaluminate catalysts in short-contact-time reactors. Hexaaluminate catalysts offer excellent high-temperature stability compared to the equivalent metal-based catalysts. The hexaaluminates are synthesized by a metal-exchange process using alumoxane precursors that enable a wide range of metal substitutions. Of all the combinations tested, RhSr-substituted hexaaluminates yielded the best performance. The catalysts are supported on alumina porous-foam structures, which are positioned within a tube furnace to control the operating temperature. Two-stage combinations of RhSr- and Ni-substituted hexaaluminates are shown to improve conversion activity and selectivity compared to a single-catalyst system. 相似文献