全文获取类型
收费全文 | 38356篇 |
免费 | 7144篇 |
国内免费 | 2577篇 |
专业分类
化学 | 22102篇 |
晶体学 | 422篇 |
力学 | 672篇 |
综合类 | 98篇 |
数学 | 364篇 |
物理学 | 24419篇 |
出版年
2024年 | 50篇 |
2023年 | 251篇 |
2022年 | 812篇 |
2021年 | 960篇 |
2020年 | 1106篇 |
2019年 | 1037篇 |
2018年 | 936篇 |
2017年 | 1191篇 |
2016年 | 1734篇 |
2015年 | 1671篇 |
2014年 | 2013篇 |
2013年 | 3028篇 |
2012年 | 2425篇 |
2011年 | 2824篇 |
2010年 | 2189篇 |
2009年 | 2700篇 |
2008年 | 2692篇 |
2007年 | 2860篇 |
2006年 | 2574篇 |
2005年 | 2082篇 |
2004年 | 1884篇 |
2003年 | 1596篇 |
2002年 | 1365篇 |
2001年 | 1107篇 |
2000年 | 1066篇 |
1999年 | 963篇 |
1998年 | 791篇 |
1997年 | 711篇 |
1996年 | 600篇 |
1995年 | 521篇 |
1994年 | 405篇 |
1993年 | 359篇 |
1992年 | 337篇 |
1991年 | 240篇 |
1990年 | 177篇 |
1989年 | 140篇 |
1988年 | 170篇 |
1987年 | 109篇 |
1986年 | 66篇 |
1985年 | 55篇 |
1984年 | 59篇 |
1983年 | 14篇 |
1982年 | 38篇 |
1981年 | 41篇 |
1980年 | 33篇 |
1979年 | 15篇 |
1978年 | 10篇 |
1976年 | 9篇 |
1973年 | 22篇 |
1971年 | 8篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
961.
The electrochemical oxidation of methanol was investigated on a Pt–Ru–Mo catalyst with an in situ infrared reflectance spectroscopy. The electrocatalysts were prepared by an electrochemical deposition and dispersed in a conducting three-dimensional matrix of polyaniline (PAni). We observed that CO2 is produced from methanol oxidation at 350 mV vs. RHE on PAni/Pt–Ru–Mo, which is 100 mV less negative than on PAni/Pt–Ru and 200 mV less than on PAni/Pt. The results suggest that Pt–Ru–Mo is less sensitive to COADS poisoning than Pt–Ru and much more sensitive than Pt. Large differences are observed concerning the average wavenumber of ADS between Pt–Ru–Mo, Pt–Ru, and Pt. 相似文献
962.
Bernhard Schrader 《Angewandte Chemie (International ed. in English)》1973,12(11):884-908
Raman spectorscopy is—like infrared spectroscopy—a method for the study of vibrations of molecules and crystals. The two methods are complementary: if a vibration results in a change of the polarizability of a molecule, it is Raman active; if a change in the molecular dipole moment results, it is infrared active Vibrations of nonpolar groups and totally symmetrical vibrations of molecules are often only Raman active. IR and Raman spectra together give information about the symmetries and structures of molecules and crystals and about the properties of chemical bonds and intermolecular interactions. Until about 10 years ago Raman spectra could only be recorded on relatively large amounts of essentially colorless substances. After the advent of laser light sources the situation changed completely. The amount of sample substance required is now in the region of milli- and micrograms. Gases, liquids and solid samples, especially air-sensitive and reactive substances, single crystals, crystal needles and filaments as well as aqueous solutions can be readily investigated. The identification of molecules and the elucidation of molecular structures, biochemical analysis, and control of evnivornmental pollution are important aplications of Raman spectroscopy. Raman spectroscopy now constitutes an additional powerful tool in instrumental analysis 相似文献
963.
The conditions of formation of complex lanthanide chromate(VI)-phosphates K2R(CrO4)(PO4) were found and these compounds were synthesized by solid-state synthesis with variation of the starting compounds, the temperature
of synthesis (500–800 °C), and the annealing time (6–200 h). These salts are typical of late lanthanides, R = Dy-Lu, Y. Using
lutetium derivatives as examples, it was shown that no similar compounds with lithium or sodium are formed. All the complex
chromate(VI)-phosphates obtained decompose under static conditions at temperatures above 550 °C. They are isostructural and crystallize
in the monoclinic system. The unit cell parameters for thulium, ytterbium, and lutetium compounds were calculated. It is shown
by IR spectroscopy that PO4 tetrahedra in the crystal lattice of potassium lanthanide chromate(VI)-phosphates are substantially distorted, whereas the CrO4 tetrahedra retain the regular tetrahedron symmetry (T
d
).
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 622–626, April, 2006. 相似文献
964.
Sulfur diisocyanate is generated from a heterogeneous reaction of gaseous sulfur dichloride with silver cyanate and studied for the first time in the gas phase. Combined with quantum chemical calculations, the electronic structure is characterized by photoelectron spectroscopy (PES). Simultaneously, an investigation of the possible ionization and dissociation processes for the molecular cation is presented based on experimental soft ionization mass spectrometry. From the calculated bond-dissociation energies, the dissociation pathway is determined. S(NCO)2+ undergoes 1,3-sigmatropic rearrangement with a smaller barrier height (9.9 kcal mol(-1)) than the neutral counterpart. Thus, the 1,3-sigmatropic rearrangement is preferred for the molecular cation, and OCNCO+ and NS+ is produced by subsequent dissociation of the rearrangement product. The analysis agrees very well with the experimental mass spectrum. 相似文献
965.
G. Bruno P. Capezzuto G. Cicala F. Cramarossa 《Plasma Chemistry and Plasma Processing》1986,6(2):109-125
Plasma-chemical reduction of SiCl4 in mixtures with H2 and Ar has been studied by optical emission spectroscopy (OES) and laser interferometry techniques. It has been found that the Ar:H2 ratio strongly affects the plasma composition as well as the deposition (r
D) and etch (r
E) rates of Si: H, Cl films and that the electron impact dissociation is the most important channel for the production of SiClx species, which are the precursors of the film growth. Chemisorption of SiClx and the reactive surface reaction SiClx+H–SiCl(x–1)0+HCl are important steps in the deposition process. The suggested deposition model givesr
D [SiClx][H], in agreement with the experimental data. Etching of Si: H, Cl films occurs at high Ar: H2 ratio when Cl atoms in the gas phase become appreciable and increases with increasing Cl concentration. The etch rate is controlled by the Cl atom chemisorption step. 相似文献
966.
The resonance Raman spectra of tris(acetylacetonatoiron(III)) and ruthenium(III) complexes in various solvents and in water-acetonitrile (W-AN) mixtures were measured. The resonance Raman spectra of both complexes indicated peaks near 460 and around 1580 cm–1. Thev(C-O) peak (around 1580 cm–1) is shifted to low frequency with an increase in the dielectric constant T of the solvents, whereas thev(M-O) (M=Fe and Ru, near 460 cm–1) are constant, independent of T. It implies that the C-O bond in the acac– ligand is lengthened by the polarizability effect of the solvents, while both the Fe-O and Ru-O bonds, which are located in the inside of the complexes, are not influenced by the solvents indicating that the interaction does not depend on the properties of individual solvent molecules but on those of the aggregate. 相似文献
967.
José Luis Vilchez Gonzalo Sánchez-Palencia Ramiro Avidad Luis Fermín Capitán-Vallvey Alberto Navalón 《Mikrochimica acta》1993,110(1-3):61-69
A method for the simultaneous determination of yohimbine and boldine in mixtures by first-derivative synchronous spectrofluorimetry has been developed. The method is based on their native fluorescence in 0.1N sulphuric acid medium. The constant wavelength difference chosen to optimize the determination was =em -em=82 nm. Yohimbine was measured at ex//em= 285/367 nm, and boldine at ex/em=272/354 nm. The range of application is 10–500 g/l for yohimbine and 1–50 g/l for boldine. The method was applied to the determination of yohimbine and boldine in synthetic mixtures and pharmaceuticals, with errors generally 2%. Relative standard deviations were about 2%.Dedicated to Professor Fermin Capitán on his 72th birthday 相似文献
968.
In the present work, corrosion resistance of surface-coated galvanized steel was quantitatively determined by an analysis
of the alternating current (AC) impedance spectra measured on the salt-spray-tested specimen. To evaluate the corrosion resistance
of the surface-coated galvanized steel, AC impedance spectroscopy was performed on the salt-spray-tested specimen previously
exposed to salt-sprayed corrosive environment. From the analysis of the impedance spectra, the area fraction transient of
white rust θ
2(t) was theoretically derived from the equivalent circuit equation by using two fitting parameters. The values of the two fitting
parameters were determined by fitting the empirical transient equations to the area fraction of the resin coating layer and
to the total resistance obtained from the impedance spectra measured, respectively. From the analyses of θ
2(t) for four kinds of surface-coated galvanized steels with various resin coating layers, it is indicated that as the values
of the two fitting parameters decrease in the order of CP, GI, OD and OM (commercial trade names) specimens, the corrosion
resistance increases in that order as well. Furthermore, from the quantitative comparison of the two fitting parameters with
the polarization resistance of the upper resin coating layer R
p determined from the potentiodynamic polarization curve, it is suggested that the two fitting parameters decrease in value
as well with increasing R
p. 相似文献
969.
Rollie J. Myers 《Journal of solution chemistry》2007,36(3):395-403
We have measured the second acid dissociation constant, K
2a
, at several ionic strengths for hydrogen telluride (H2Te) using the Charge Transfer to Solvent (CTTS) uv spectra of its anions HTe− and Te2−. Since it is produced in our solutions, we have also determined the spectra of Te2
2− both in the uv and in the visible regions. At 25 ∘C, K
2a
= (1.28 ± 0.02) × 10−12 by extrapolation to zero ionic strength. Its value at an ionic strength equal to 0.5 mol.dm-3 was estimated to be (8.7 ± 0.2) × 10−12. The solution thermodynamics of these species are also discussed and comparisons are made to related acids. 相似文献
970.