全文获取类型
收费全文 | 3710篇 |
免费 | 291篇 |
国内免费 | 383篇 |
专业分类
化学 | 3449篇 |
晶体学 | 62篇 |
力学 | 21篇 |
综合类 | 13篇 |
数学 | 4篇 |
物理学 | 835篇 |
出版年
2024年 | 6篇 |
2023年 | 53篇 |
2022年 | 45篇 |
2021年 | 68篇 |
2020年 | 121篇 |
2019年 | 87篇 |
2018年 | 81篇 |
2017年 | 74篇 |
2016年 | 122篇 |
2015年 | 129篇 |
2014年 | 159篇 |
2013年 | 264篇 |
2012年 | 306篇 |
2011年 | 218篇 |
2010年 | 159篇 |
2009年 | 234篇 |
2008年 | 234篇 |
2007年 | 245篇 |
2006年 | 242篇 |
2005年 | 194篇 |
2004年 | 191篇 |
2003年 | 183篇 |
2002年 | 135篇 |
2001年 | 92篇 |
2000年 | 115篇 |
1999年 | 107篇 |
1998年 | 93篇 |
1997年 | 73篇 |
1996年 | 64篇 |
1995年 | 63篇 |
1994年 | 40篇 |
1993年 | 37篇 |
1992年 | 39篇 |
1991年 | 28篇 |
1990年 | 18篇 |
1989年 | 13篇 |
1988年 | 14篇 |
1987年 | 10篇 |
1986年 | 6篇 |
1985年 | 6篇 |
1984年 | 3篇 |
1983年 | 1篇 |
1982年 | 3篇 |
1980年 | 4篇 |
1979年 | 3篇 |
1977年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有4384条查询结果,搜索用时 31 毫秒
71.
含Cu复合氧化物对NO和CO吸附和活化的TPSR研究 总被引:2,自引:2,他引:2
利用MS-TPD法并结合XRD、化学分析等对催化剂进行了表征,探讨了K2NiF4结构La2-x(Sr,Th)xCuO4±λ系催化剂中三个典型样品LaSrCuO4、La2CuO4和La1.7Th0.3CuO4对NO、CO及CO+NO等小分子的吸附性能和活化规律。结果表明:NO吸附量的大小与催化剂中氧空位含量有关,吸附强度和脱附峰种类与金属离子氧化态有关。CO在氧缺陷复合氧化物催化剂上的吸附是首先变为碳酸根,并在高温以CO2物种脱出.在NO和CO的共吸附过程中,有关NO的吸、脱性能与单独NO-TPD中NO的吸脱附规律相似,表明NO在NO+CO共吸附的竞争吸附过程中,优先吸附起决定作用,而受CO的影响较小.NO的吸附是NO活化分解的必要条件. 相似文献
72.
V. A. Startseva L. E. Nikitina N. P. Artemova S. A. Dieva V. V. Plemenkov 《Chemistry of Natural Compounds》2000,36(6):587-589
Ethanedithiol and di(mercaptoethyl)sulfide react regio- and stereoselectively with (+)-3-carene and -hydroxy(-)--pinene -oxides in the presence of sodium ethoxide to give the corresponding bis- and tris-sulfides with two terpene fragments 相似文献
73.
Zr0.5Ti0.5O2(ZT) and Zr0.25Ti0.25Al0.5O2(ZTA) mixed oxides were prepared by co-precipitation method and characterized by low temperature adsorption-desorption, XRD and NH3-TPD. The activity of Pt/Zr0.5Ti0.5O2 and Pt/ Zr0.5Ti0.5Al0.5O2 catalysts was evaluated using the simulated gases. The results show that ZTA samples exhibit higher specific surface area, larger pore volume and proper surface acidic amount and acidity in comparison with ZT. The results of the catalytic test indicate that Pt/ZT and Pt/ZTA catalysts exhibit excellent low-temperature catalytic activity and lower light-off temperatures of hydrocarbon, carbon monoxide and nitrogen oxides, especially better conversion for nitrogen oxides (NOx). The addition of Al2O3 into ZT enhanced the anti-aging property of Pt/ ZTA catalysts due to the excellent textural, structural, surface acidity and thermal stability. 相似文献
74.
Li-Ya Wang Xiao-Qiang Wang Kai Jiang Jiu-Li Chang Yu-Fang Wang 《Journal of Molecular Structure》2007,840(1-3):14-21
A new nitronyl nitroxide NIT2-bithph (1) and its manganese(II) compound [Mn(hfac)2(IMHBithph)]2·(NIT2-bithph)(C6H14) (2) (hfac = hexafluoroacetylacetonate; NIT2-bithph = 4,4,5,5-tetramethyl-2-(bithiophenal-2-yl)imidazoline-1-oxyl-3-oxide; IMHBithph = 1-hydroxy-2-bithiophenal-4,4,5,5-tetramethyl-4,5-dihydro- 1H-imidazole) have been synthesized and structurally characterized by X-ray diffraction methods. The units of compound 1 were connected as one-dimensional chain by the intermolecular hydrogen bonds which afford an intermolecular antiferromagnetic interaction between nitronyl nitroxide radicals within the chain (J = −1.89 cm−1). Compound 2 resulting from the reaction of Mn(hfac)2·2H2O and NIT2-bithph is dinuclear and includes the reduced amidino-oxide form of NIT2-bithph, it is made up of three parts: a [Mn(hfac)2(IMHBithph)]2 dimer unit, an uncoordinated NIT2-bithph radical and a noncoordinated solvent molecule of hexane, the molecule of radical is hydrogen bonded to its reduced form. Two reduced IMHBithph ligands bridge the two manganese(II) ions through their amidino-oxide oxygen atoms resulting in a small intramolecular antiferromagnetic interaction between the manganese ions (J = −1.55 cm−1). 相似文献
75.
76.
Donia A. M. El-Boraey H. A. El-Samalehy M. F. 《Journal of Thermal Analysis and Calorimetry》2003,73(3):987-1000
Manganese and iron complexes of Schiff bases derived from 6-formylkhellin were prepared and characterized. Complexes of o-phenylenediamine derivative (ligand (I)) are monomeric or dimeric whereas those of p-phenylenediamine derivative (ligand (II)) are polymeric. The complexes obtained are characterized by a lower magnetic moment
values. The complexes also have different solvent of crystallization with different nature of interaction. The thermal behaviour
of the ligands and their metal complexes was investigated by means of DTA, TG, IR and X-ray diffraction spectroscopy. Ligand
(I) shows different thermal behaviour from that of ligands (II) and (III). The complexes of ligand (II) give abnormal oxides
as a final product during their thermal decomposition.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
77.
A rapid and simple method, the so-called stearic acid method (SAM) was developed to prepare nanostructured TiO2/SnO2 binary oxides by combustion of stearic acid precursors. The preparative process was studied by Fourier transform infrared spectroscopy (FT-IR). During the preparative process, metal precursors were dispersed in stearic acid at molecular level. Microstructure of the samples was investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), BET specific surface area measurement and the results were compared with those obtained by conventional sol-gel method. The photocatalytic decomposition of methyl orange was used as a model system to determine the relative influences of the preparation method and the concentration of SnO2 on the photocatalytic activities. It was found that preparative methods affected the crystalline structure of TiO2/SnO2 powders and the anatase phase of TiO2 was stabilized by the addition of SnO2 in SAM. The samples prepared by SAM showed better dispersity, larger specific surface area and the TiO2/SnO2 (r=0.15, SAM) catalyst showed higher photocatalytic activity than Degussa P25. 相似文献
78.
V. S. Lenenko P. Kränke M. Wahren V. B. Shur M. E. Vol'pin 《Russian Chemical Bulletin》1995,44(7):1293-1299
The interaction of labeled dinitrogen complexescis-(Me2PhP)4Mo(15N2)2 andtrans-(dppe)2W(15N2)2 with non-labeled nitronium and nitrosonium fluoroborates,14NO2BF4 and14NOBF4, in sulfolane at room temperature in the presence of H2SO4 results in rapid formation of labeled nitrous and nitric oxides (15N14NO,15NO), as well as15N14N. The yield of the products depends on the reagent ratio and reaches 10–20 mol. % per mole of a complex under optimum conditions. The mechanism of the reactions found is proposed. It involves the step of protonation of the dinitrogen ligand to form the corresponding hydrazido(2–) derivatives, which are then attacked by nitronium or nitrosonium cations. In accordance with the mechanism proposed, it was established that the hydrazido(2–) complexes, (Me2PhP)3Mo(15N2H2)Cl2 and (dppe)2W(15N2H2)Cl2, are capable of forming15N14NO,15NO, and15N14N under the action of14NO2BF4 and14NOBF4 in the absence of an acid.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 13–13, July, 1995. 相似文献
79.
基于Mn(Ⅱ)对试剂2-(8'-羟基喹啉-5'-磺基-7'-偶氮基)-1-羟基-8-氨基一萘二磺酸(以下简称HQSAH)分解反应的催化作用,提出了锰的荧光催化动力学分析新方法,其λex/em=230/415nm,适宜酸度范围为pH11.0~12.0,Mn(Ⅱ)含量在0~0.08μg/mL呈线性关系,该法用于分析铸造铝合金中的痕量锰,效果良好。还初步探讨了反应机制,确定了反应动力学方程,测定了反应速率和活化能。 相似文献
80.
MgAl2O4:Mn phosphors have been prepared at 500 °C by combustion route. Powder X-ray diffraction (XRD) indicated the presence of mono-MgAl2O4 phase. Scanning electron microscopy showed that the powder particle crystallites are mostly angular. Fourier transform infrared spectroscopy confirmed the presence of AlO6 group which makes up the MgAl2O4 spinel. Photoluminescence studies showed green/red emission indicating that two independent luminescence channels in this phosphor. The green emission at 518 nm is due to 4T1 → 6A1 transition of Mn2+ ions. The emission at 650 nm is due to the charge-transfer deexcitation associated with the Mn ion. EPR spectrum exhibits allowed and forbidden hyperfine structure at g=2.003. The g≈2.00 is due to Mn2+ ion in an environment close to tetrahedral symmetry. It is observed that N and χ increase with decrease of temperature obeying the Boltzmann law. The variation of zero-field splitting parameter (D) with temperature is evaluated and discussed. 相似文献