全文获取类型
收费全文 | 2631篇 |
免费 | 160篇 |
国内免费 | 259篇 |
专业分类
化学 | 1380篇 |
晶体学 | 92篇 |
力学 | 131篇 |
综合类 | 5篇 |
数学 | 345篇 |
物理学 | 1097篇 |
出版年
2024年 | 14篇 |
2023年 | 89篇 |
2022年 | 61篇 |
2021年 | 51篇 |
2020年 | 68篇 |
2019年 | 78篇 |
2018年 | 50篇 |
2017年 | 63篇 |
2016年 | 102篇 |
2015年 | 81篇 |
2014年 | 144篇 |
2013年 | 135篇 |
2012年 | 126篇 |
2011年 | 189篇 |
2010年 | 201篇 |
2009年 | 198篇 |
2008年 | 171篇 |
2007年 | 211篇 |
2006年 | 158篇 |
2005年 | 139篇 |
2004年 | 129篇 |
2003年 | 101篇 |
2002年 | 61篇 |
2001年 | 53篇 |
2000年 | 49篇 |
1999年 | 49篇 |
1998年 | 50篇 |
1997年 | 46篇 |
1996年 | 38篇 |
1995年 | 22篇 |
1994年 | 21篇 |
1993年 | 17篇 |
1992年 | 11篇 |
1991年 | 11篇 |
1990年 | 9篇 |
1989年 | 14篇 |
1988年 | 9篇 |
1987年 | 1篇 |
1986年 | 6篇 |
1985年 | 5篇 |
1984年 | 1篇 |
1983年 | 2篇 |
1982年 | 5篇 |
1981年 | 3篇 |
1980年 | 1篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1977年 | 4篇 |
排序方式: 共有3050条查询结果,搜索用时 15 毫秒
1.
Wacker oxidation is an industry-adopted process to transform olefins into value-added epoxides and carbonyls. However, traditional Wacker oxidation involves the use of homogeneous palladium and copper catalysts for the olefin addition and reductive elimination. Here, we demonstrated an ultrahigh loading Cu single atom catalyst(14% Cu, mass fraction) for the palladium-free Wacker oxidation of 4-vinylanisole into the corresponding ketone with N-methylhydroxylamine hydrochloride as an additive under mild conditions. Mechanistic studies by 18O and deuterium isotope labelling revealed a hydrogen shift mechanism in this palladium-free process using N-methylhydroxylamine hydrochloride as the oxygen source. The reaction scope can be further extended to Kucherov oxidation. Our study paves the way to replace noble metal catalysts in the traditional homogeneous processes with single atom catalysts. 相似文献
2.
Molecular electroactive monolayers have been produced from vinylferrocene (VFC) via light-assisted surface anchoring to H-terminated n- and p-Si(1 0 0) wafers prepared via wet chemistry, in a controlled atmosphere. The resulting Si-C bound hybrids have been characterized by means of XPS and AFM. Their performance as semiconductor functionalized electrodes and their surface composition have been followed by combining electrochemical and XPS measurements on the same samples, before and after use in an electrochemical cell. White-light photoactivated anchoring at short (1 h) exposure times has resulted in a mild route, with a very limited impact on the initial quality of the silicon substrate. In fact, the functionalized Si surface results negligibly oxidized, and the C/Fe atomic ratio is close to the value expected for the pure molecular species. The VFC/Si hybrids can be described as (η5-C5H5)Fe2+(η5-C5H4)-CH2-CH2-Si species, on the basis of XPS results. Electrochemical methods have been applied in order to investigate the role played by a robust, covalent Si-C anchoring mode towards substrate-molecule electronic communication, a crucial issue for a perspective development of molecular electronics devices. The response found from cyclic voltammograms for p-Si(1 0 0) functionalized electrodes, run in the dark and under illumination, has shown that the electron transfer is not limited by the number of charge carriers, confirming the occurrence of electron transfer via the Si valence band. The hybrids have shown a noticeable electrochemical stability and reversibility under cyclic voltammetry (cv), and the trend in peak current intensity vs. the scan rate was linear. The molecule-Si bond is preserved even after thousands of voltammetric cycles, although the surface coverage, evaluated from cv and XPS, decreases in the same sequence. An increasingly larger surface concentration of Fe3+ at the expenses of Fe2+ redox centers has been found at increasing number of cv’s, experimentally associated with the growth of silicon oxide. Surface SiO− groups from deprotonated silanol termination, induced by the electrochemical treatments, are proposed as the associated counterions for the Fe3+ species. They could be responsible for the observed decrease in the electron transfer rate constant with electrode ageing. 相似文献
3.
Fe2(CO)6(μ-S2) was used as a single source precursor in attempt to produce FeS film via MOCVD. Pyrolysis of Fe2(CO)6(μ-S2) at temperature below 500℃ produced Fe1-xS or Fe7S8 powder as indicated by its powder X-ray spectra. At 750 ℃, polycrystalline FeS powder was obtained. In film deposition, polycrystalline Fe1-xS or Fe7Ss films were obtained on Si(100) and Ag/Si(100) substrates below 500 ℃. SEM micrographs showed the film on Si(100) substrate containing whisker like grains. However, pillar like grains were obtained on Ag/Si(100) substrate.Deposition rates are also different for different substrates as evaluated by the thickness of the films, which were obtained by SEM micrographs of the cross section of the films. At 750℃, similar polycrystalline Fe1-xS or Fe7S8 film was obtained. 相似文献
4.
Vincent Maurice 《Surface science》2005,581(1):88-104
STM, STS, LEED and XPS data for crystalline θ-Al2O3 and non-crystalline Al2O3 ultra-thin films grown on NiAl(0 0 1) at 1025 K and exposed to water vapour at low pressure (1 × 10−7-1 × 10−5 mbar) and room temperature are reported. Water dissociation is observed at low pressure. This reactivity is assigned to the presence of a high density of coordinatively unsaturated cationic sites at the surface of the oxide film. The hydroxyl/hydroxide groups cannot be directly identify by their XPS binding energy, which is interpreted as resulting from the high BE positions of the oxide anions (O1s signal at 532.5-532.8 eV). However the XPS intensities give evidence of an uptake of oxygen accompanied by an increase of the surface coverage by Al3+ cations, and a decrease of the concentration in metallic Al at the alloy interface. A value of ∼2 for the oxygen to aluminium ions surface concentration ratio indicates the formation of an oxy-hydroxide (AlOxOHy with x + y ∼ 2) hydroxylation product. STM and LEED show the amorphisation and roughening of the oxide film. At P(H2O) = 1 × 10−7 mbar, only the surface of the oxide film is modified, with formation of nodules of ∼2 nm lateral size covering homogeneously the surface. STS shows that essentially the valence band is modified with an increase of the density of states at the band edge. With increasing pressure, hydroxylation is amplified, leading to an increased coverage of the alloy by oxy-hydroxide products and to the formation of larger nodules (∼7 nm) of amorphous oxy-hydroxide. Roughening and loss of the nanostructure indicate a propagation of the reaction that modifies the bulk structure of the oxide film. Amorphisation can be reverted to crystallization by annealing under UHV at 1025 K when the surface of the oxide film has been modified, but not when the bulk structure has been modified. 相似文献
5.
Based. On the effective Hamiltonian with the generalized factorization approach, we calculate the branchingratios and CP asymmetries of B → VV decays in the Topcolor-assisted Technicolor (TC2) model. Within the consideredparameter space we find that: (a) for the penguin-dominated B → K* φ and K*0 φ decays, the new physics enhancementsto the branching ratios are around 40%; (b) the measured branching ratios of B →K* φ and K*0φ decays prefer therange of 3 Neffc 5; (c) the SM and TC2 model predictions for the branching ratio B(B →ρ ρ0) are only about halfof the Belle‘s measurement; and (d) for most B → VV decays, the new physics corrections on their CP asymmetries are generally small or moderate in magnitude and insensitive to the variation of mπ and Neffc. 相似文献
6.
在研究大量实验曲线的基础上,指出势阱所有能级均有一定的宽度,电子或空穴在各能级中出现的概率符合正态分布,从理论上分析了I类超晶格和双势垒单势阱的发光光谱与吸收光谱·解释了GaAs/Ga1-xAlxAs多量子阱和超晶格吸收光谱吸收边及量子阱变窄时各吸收峰的“蓝移现象”及GaAs/Ga1-xAlxAs双势垒单量子阱样品的电流—电压特性曲线及电导—电压特性曲线的特征和出现的“负阻效应”· 相似文献
7.
WANG Jiang-yun GU Wen WANG Wen-zhen LIU Xin LIAO Dai-zheng 《高等学校化学研究》2006,22(3):283-286
Introduction Itiswell knownthatcyanogroupsincyanometa latessuchas[Ag(CN)2]-unitscanbeusedasbridg ingligandsandapolymericstructurecanbeformed throughsilver silver(argentophilic)interactions.This propertyhasbeenexploredintheconstructionofmany oligomericandp… 相似文献
8.
Christian Erich Zybill Mahmoud Abdel-Hafiez Sami Allam Tharwat El Sherbini 《Progress in Solid State Chemistry》2007,35(2-4):469-480
Ferroelectric thin films form an equilibrium domain structure compatible with their respective crystallographic symmetry. In tetragonal (111) PZT, 90° domains prevail; in (pseudo-tetragonal) (100) SBT both 90° and 180° domains are present. The size of 90° domains has been measured for e.g., PZT as slabs of 15 nm width. Domain size is a result of stress minimization in the film during the paraelectric (PE) → ferroelectric (FE) transition. A precise and regular domain pattern for (111) PZT and (100) SBT films has been investigated in detail by TMSFM. Single domains can be addressed mechanically with the tip of an AFM. Such single domain switching corresponds to a data storage density of 200 Gbit/inch2. Applications of ferroelectric and high- paraelectric materials for e.g., non-volatile data storage replacing DRAM devices or as sensors in infrared cameras are increasingly becoming popular. 相似文献
9.
Mössbauer spectroscopy with 57Fe (119Sn) probe layers is a useful method to study the local magnetic structures at buried interfaces. However interface alloying, which always exists in the real samples, have to be taken into account for accurate interpretation of experimental data. We developed an algorithm, which describes the interface intermixing in the multilayers. Substituting deposited atoms by atoms of substrate and floating of deposited atoms in the upper layers during epitaxial growth leads to the formation of asymmetric chemical and magnetic interfaces. This asymmetry in the M1/M2 superlattices can explain the difference between magnetic responses from M1 on M2 and M2 on M1 interfaces which were observed in experiments. Applying this intermixing model to the systems with probe layers located at different distances from the interfaces gives the natural explanation of hyperfine fields distributions on probe atoms and helps us clarify some discrepancies reported in the literature. 相似文献
10.
The problem treated in this paper concerns calculating the evolution of the pressure in a single-phase, slightly compressible fluid in a porous medium consisting of communicating layers. The fluid is produced through a point sink located on the side of an otherwise sealed cylindrical wellbore. This location of the sink causes the flow around the wellbore to be azimuthally asymmetric.The problem is solved through successive application of Laplace, finite Fourier and finite Hankel transforms. Although apparently straightforward, this approach leads to serious numerical difficulties. The published form of the inversion formula for the finite Hankel transform leads to inaccurate computation for the higher azimuthal modes even with 128 bit arithmetic. An alternative form is developed which enables accurate evaluation of the solution with the more practical 64 bit arithmetic. The technique for two-layer solution presented here can be directly extended to a problem with a larger number of communicating layers. This is the first instance of successful application of the finite Hankel transform to an azimuthally asymmetric diffusion problem. 相似文献