全文获取类型
收费全文 | 1919篇 |
免费 | 95篇 |
国内免费 | 9篇 |
专业分类
化学 | 1324篇 |
晶体学 | 14篇 |
力学 | 20篇 |
数学 | 155篇 |
物理学 | 319篇 |
无线电 | 191篇 |
出版年
2023年 | 18篇 |
2022年 | 57篇 |
2021年 | 63篇 |
2020年 | 36篇 |
2019年 | 42篇 |
2018年 | 40篇 |
2017年 | 27篇 |
2016年 | 72篇 |
2015年 | 75篇 |
2014年 | 68篇 |
2013年 | 111篇 |
2012年 | 127篇 |
2011年 | 158篇 |
2010年 | 74篇 |
2009年 | 82篇 |
2008年 | 140篇 |
2007年 | 110篇 |
2006年 | 77篇 |
2005年 | 103篇 |
2004年 | 81篇 |
2003年 | 58篇 |
2002年 | 64篇 |
2001年 | 27篇 |
2000年 | 32篇 |
1999年 | 21篇 |
1998年 | 15篇 |
1997年 | 12篇 |
1996年 | 20篇 |
1995年 | 10篇 |
1994年 | 19篇 |
1993年 | 19篇 |
1992年 | 21篇 |
1991年 | 11篇 |
1990年 | 25篇 |
1989年 | 12篇 |
1988年 | 14篇 |
1987年 | 12篇 |
1986年 | 14篇 |
1985年 | 5篇 |
1984年 | 2篇 |
1983年 | 5篇 |
1982年 | 7篇 |
1981年 | 9篇 |
1980年 | 2篇 |
1979年 | 5篇 |
1978年 | 3篇 |
1976年 | 5篇 |
1974年 | 4篇 |
1973年 | 3篇 |
1935年 | 1篇 |
排序方式: 共有2023条查询结果,搜索用时 15 毫秒
21.
22.
Sol-gel Cu//MgOSiO2 catalysts were prepared gelling tetraethoxysilane (TEOS), magnesium ethoxide and copper acetylacetonate at pH 3 and pH 9. The catalysts shown specific surface areas ca. 500 m2/g and 140 m2/g for pH 9 and pH 3 preparations respectively. Si(OH) and Si(OH)2 hydroxy groups were observed by MAS-RMN spectroscopy in both preparations. CO2-TPD and NH3-TPD desorption thermograms showed that acid and basic sites were formed on the catalysts surface. It has been found that the catalysts having the highest density of basic sites were the catalysts showing the highest activity for the CO oxidation. It is proposed that the catalytic activity depends of the relative Cu=1/Cu=2 stability given by the support acidity. 相似文献
23.
Sonia Jam Masume Ghalbi Ahangary Ahmad Tavasoli Kambiz Sadaghiani Ali Nakhaei Pour 《Reaction Kinetics and Catalysis Letters》2006,89(1):71-79
Summary An integrated process for producing liquid fuels from synthesis gas via a two-stage Fischer-Tropsch (FT) reaction is disclosed. An iron catalyst was used in the first bed of a fixed-bed reactor
followed by a ruthenium promoted cobalt catalyst in the second bed. The activity and selectivity of the dual-bed system were
assessed and compared with those using catalysts in a single bed system, separately. The methane selectivity in the dual-bed
reactor was about 11% less compared to that of the single-bed system. The C5+ selectivity for the dual-bed reactor was 19.7% higher than that of the single-bed system. 相似文献
24.
P. Quevauviller M. Lachica E. Barahona A. Gomez G. Rauret A. Ure H. Muntau 《Fresenius' Journal of Analytical Chemistry》1998,360(5):505-511
Single extraction tests are commonly used to study the eco-toxicity and mobility of metals in soils, e.g. to assess the bioavailable
metal fraction (and thus to estimate the related phyto-toxic and nutritional deficiency effects) and the environmentally accessible
trace metals upon disposal of e.g. sediment on to a soil (e.g. contamination of ground waters). However, the lack of uniformity
in the different procedures does not allow the results to be compared worldwide nor the procedures to be validated. This paper
describes the interlaboratory testing of EDTA- and DTPA-extraction procedures for soil analysis, followed by the preparation
of a calcareous soil reference material (CRM 600), the homogeneity and stability studies and the analytical work performed
for the certification of the EDTA- and DTPA- extractable contents of some trace metals (following the standardized extraction
procedures).
Received: 21 May 1997 / Revised: 4 July 1997 / Accepted: 9 July 1997 相似文献
25.
A new chemical method is reported for the determination of total fluoride in complex liquids and suspensions, such as fruit juices, urine, serum and blood. It is based on the formation of the A1F radical in a graphite furnace afterin situ oxygen-assisted ashing of the untreated sample. The absorbance of this radical is measured at 227.45 nm. The method is relatively easy to use and provides a low detection limit (14 ng/ml) and reasonable reproducibility (5–10%). 相似文献
26.
First-order relativistic corrections to the energy of closed-shell molecular systems are calculated, using all terms in the two-component Breit-Pauli Hamiltonian. In particular, we present the first implementation of the two-electron Breit orbit-orbit integrals, thus completing the first-order relativistic corrections within the two-component Pauli approximation. Calculations of these corrections are presented for a series of small and light molecules, at the Hartree-Fock and coupled-cluster levels of theory. Comparisons with four-component Dirac-Coulomb-Breit calculations demonstrate that the full Breit-Pauli energy corrections represent an accurate approximation to a fully relativistic treatment of such systems. The Breit interaction is dominated by the spin-spin interaction, the orbit-orbit interaction contributing only about 10% to the total two-electron relativistic correction in molecules consisting of light atoms. However, the relative importance of the orbit-orbit interaction increases with increasing nuclear charge, contributing more than 20% in H(2)S. 相似文献
27.
The methods usually used to determine the ratio metal-ligand in inorganic complexes require a set of solutions with different concentrations for both the ligand and metal. We propose a new method using the total reflection X-ray fluorescence technique, in which the ratio between metal and ligand is determined precisely, easily, and quickly. Experimental results provide evidence that for different chemical complexes, the ligand-metal ratio determined by this technique deviates at most from stoichiometric values by 6%. The technique is restricted usually to elements with Z above 14, and its detection limit is on the order of 10(-8) g/g. 相似文献
28.
Sonia E. Blanco 《Tetrahedron letters》2007,48(14):2577-2581
By applying the B3LYP/6-31G(d) method with the SCIPCM model on seven 4X substituted 2-hydroxybenzaldehydes, some structural characteristics related with their conformational equilibria and intramolecular hydrogen bonds have been clarified. The compounds are almost completely under the planar conformation characterized by a strong intramolecular hydrogen bond, which decreases in those solvents that possess a higher hydrogen bond donating capability and polarity. The substituents exert a marked influence on the conformational equilibrium constants and the strength of the IHB. Moreover, the excellent Hammett-type equations obtained support the proposed conformational reactions to quantify the IHB in the o-hydroxybenzaldehydes studied. 相似文献
29.
Pérez J Morales D Nieto S Riera L Riera V Miguel D 《Dalton transactions (Cambridge, England : 2003)》2005,(5):884-888
Cationic complexes [Mo(eta(3)-allyl)(CO)2L3]+ (L3 = either nitrogen-donor tridentate ligand or three monodentate ligands) were prepared in high yield and under mild conditions using as precursors either the triflato complex [Mo(eta(3)-allyl)(OTf)(CO)2(NCMe)2] or the combination of the chloro complex [Mo(eta(3)-allyl)Cl(CO)2(NCMe)2] and the salt NaBAr'(4)(Ar'= 3,5-bis(trifluoromethyl)phenyl). The tridentate ligands employed were 2,2':6',2'-terpyridine (terpy) and cis,cis-1,3,5-cyclohexanetriamine (CHTA), whereas the monodentate ligands imidazole (im) and 3,5-dimethylpyrazole (dmpz) were chosen. In order to stabilize the labile intermediates, an excess of acetonitrile was used in most of the syntheses. However, the pyrazole complex was prepared through a nitrile-free route to avoid reactions at the coordinated nitrile. The solid state structures of [Mo(eta(3)-methallyl)(CO)2(terpy)]OTf (2), [Mo(eta(3)-methallyl)(CO)2(CHTA)]BAr'4 (3), [Mo(eta(3)-methallyl)(CO)2(NCMe)3]BAr'4 (4), [Mo(eta(3)-allyl)(CO)2(im)3]OTf (5) and [Mo(eta(3)-allyl)(CO)2(dmpz)3]BAr'4 (6) were determined by means of single-crystal X-ray diffraction. 相似文献
30.
Two different versions, relativistic and nonrelativistic, of the “shape-consistent” effective potential (EP ) formalism are analyzed in ab initio calculations for transition metals. The influence of alternative core/valence partitions on the reliability of the procedure is discussed. The accuracy of EP results for transition metals is shown to depend on adequate choices of the valence subspace and proper inclusion of relativistic effects. 相似文献