全文获取类型
收费全文 | 3515篇 |
免费 | 126篇 |
国内免费 | 844篇 |
专业分类
化学 | 4074篇 |
晶体学 | 15篇 |
力学 | 8篇 |
综合类 | 13篇 |
数学 | 11篇 |
物理学 | 364篇 |
出版年
2024年 | 11篇 |
2023年 | 51篇 |
2022年 | 99篇 |
2021年 | 94篇 |
2020年 | 86篇 |
2019年 | 85篇 |
2018年 | 76篇 |
2017年 | 97篇 |
2016年 | 118篇 |
2015年 | 124篇 |
2014年 | 145篇 |
2013年 | 234篇 |
2012年 | 181篇 |
2011年 | 173篇 |
2010年 | 115篇 |
2009年 | 179篇 |
2008年 | 186篇 |
2007年 | 260篇 |
2006年 | 175篇 |
2005年 | 209篇 |
2004年 | 188篇 |
2003年 | 170篇 |
2002年 | 177篇 |
2001年 | 155篇 |
2000年 | 136篇 |
1999年 | 144篇 |
1998年 | 128篇 |
1997年 | 98篇 |
1996年 | 100篇 |
1995年 | 90篇 |
1994年 | 85篇 |
1993年 | 74篇 |
1992年 | 51篇 |
1991年 | 43篇 |
1990年 | 35篇 |
1989年 | 34篇 |
1988年 | 23篇 |
1987年 | 12篇 |
1986年 | 8篇 |
1985年 | 8篇 |
1984年 | 5篇 |
1982年 | 7篇 |
1981年 | 4篇 |
1980年 | 3篇 |
1979年 | 4篇 |
1978年 | 2篇 |
1976年 | 1篇 |
1971年 | 1篇 |
1970年 | 1篇 |
排序方式: 共有4485条查询结果,搜索用时 0 毫秒
1.
提出用溶胶粒子表面修饰方法,结合溶胶凝胶技术制备无机催化膜.该方法的基本原理是利用合适的金属配合物在胶粒表面的吸附作用,经溶胶凝胶过程,将活性组分结合到无机膜中.实验测定结果表明:(NiEDTA)2-,VO-3,MoO2-4,(Pd(NH3)4)2+,PdCl2-4,PtCl2-6和RhCl3-6可用来修饰AlOOH溶胶.以Pd/γAl2O3催化膜的制备为例,经三次溶胶凝胶过程,可制得无裂缺的厚度为9μm的Pd/γAl2O3催化膜,膜材料的平均孔直径为6nm,Pd被均匀地分布在膜的顶层,其平均粒径为23nm. 相似文献
2.
The characterization of the clusters formed on alkaline hydrolysis of [PdCl4]2– was performed using17O,23Na,35Cl,133Cs NMR and UV spectroscopy. The chemical composition of the clusters was found to be [Pd(OH)2]
n
·nNaCl. No mononuclear oxo- or hydroxocomplexes were detected. The spatial structure of the clusters is stabilized by alkali metal cations.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 675–679, April, 1993. 相似文献
3.
A new family of positive photosensitive polyimide (PPI) systems composed of solvent soluble polyimides (Pls) with cyclobutane (CBDA) structures and diazonaphthoquinone compounds (DNQ) has been prepared. Heat and catalytic imidizations were carried out to obtain CBDA Pls; the former was better than the latter in controlling the molecular weight of the Pl. The ? OH groups in the Pls were easily acetylated during catalytic imidization, so ? COOH groups were selected as weak acidic groups in the Pls. The ? COOH groups were also effective in giving the Pls an alkaline solubility. Therefore, Pls having ? COOH groups were superior to those having ? OH groups for PPI systems. The photosensitive properties of various PPl systems containing ? COOH were found to vary with the fraction of ? COOH groups in the Pls, the content of DNQ in the systems, and the molecular weight of the Pls. 相似文献
4.
Shufeng Zuo 《Applied Surface Science》2006,253(5):2508-2514
Al-pillared clays supported rare earths (RE/Al-PILC) are prepared and used as supports of palladium catalysts for deep oxidation of low concentrations of benzene (130-160 ppm). The supports and catalysts are characterized by X-ray powder diffraction (XRD), FT-IR, BET, transmission electron microscopy (TEM) and temperature-programmed reduction (H2-TPR). The results show that Al-pillaring results in a strong increase in the basal spacing (d0 0 1) from about 1.2 to 1.8 nm, and an increase in the BET surface area from 63.6 (±3.2) to 238.8 (±11.9) m2/g. Activity tests of deep oxidation of low concentration benzene show catalysts supported on Al-PILC and RE/Al-PILC are obviously more active than that on raw clay. Pd/6% Ce/Al-PILC, in particular, can catalyze the complete oxidation of low concentration benzene at a temperature as low as about 290 °C. 相似文献
5.
The aldol products derived from sulfur- or selenium containing acceptors were prepared by kinetic resolution in the presence of antibody 84G3 with enantiomeric excesses ranging from 56 to 70%. Much higher level of enantioselectivity was obtained (enantiomeric excesses all superior to 96%) for sulfanyl aldol products derived from thiomethoxyacetone with three different acceptors. 相似文献
6.
催化荧光法测定痕量草酸 总被引:3,自引:0,他引:3
在硫酸介质中 ,草酸能催化重铬酸钾氧化罗丹明B褪色 ,使体系荧光猝灭 ,建立了催化荧光法测定草酸的新方法。催化反应在 50℃水浴中进行 1 0min ,为假零级反应。测定草酸的线性范围为 0 4~ 1 2 0mg·L- 1 ,其回归方程为ΔF =8 42c(mg·L- 1 ) 3 81 ,r=0 9983 ,检出限为 0 1 6mg·L- 1 。试验了 30种共存物质的干扰情况。此法用于生物样品中草酸含量的测定 ,结果满意。 相似文献
7.
Vandana Singh Ashutosh TiwariDevendra Narayan Tripathi Tulika Malviya 《Tetrahedron letters》2003,44(39):7295-7297
O-Methylation is of outstanding importance in structural polysaccharide chemistry. A novel method for the methylation of polysaccharides using microwave (MW) irradiation is described. Seed gum from Cyamopsis tetragonolobus (Guar) was fully methylated with dimethyl sulphate and sodium hydroxide using 100% microwave power for 4 min in 68% yield. The completely methylated seed gum thus obtained was hydrolyzed by 70% formic acid followed by 0.5N H2SO4 under full microwave power for 1.16 and 1.66 min, respectively. The partially methylated monosaccharides were separated and identified. 相似文献
8.
Dmitry Yu. Murzin 《Reaction Kinetics and Catalysis Letters》2007,90(2):225-232
Reaction route analysis is applied to visualize reaction networks in several heterogeneous catalytic reactions. Combination
of the theory of complex reactions with the notion of catalytic cycles results in a topological representation of complex
mechanisms with the nodes comprising all possible surface species including free sites and branches indicating interconnections
between reactions. 相似文献
9.
V. Badescu M. Radu M. Zaharescu A. Vasilescu 《Journal of Sol-Gel Science and Technology》1994,2(1-3):43-49
Gas-chromatography coupled with mass spectrometry was used to investigate the hydrolysis and condensation of tetra-ethoxysilane (TEOS) in nonparental solvents (MeOH and nPrOH). In the presence of nonparental solvents, the reaction that advanced at highest rate is alkoxy group scrambling, that changes the precursor at the molecular level. Subsequent stages of hydrolysis-polycondensation process are essentially determined by the reactivity of the new molecular species formed. 相似文献
10.
Dehydrogenation of alcohols into aldehydes and ketones by Ru3(CO)12/PPh3 based homogeneous catalysis has been investigated as an alternative for the classical Oppenauer oxidation. Several catalytic systems have been screened in the Oppenauer-like oxidation of alcohols. A systematic study of various combinations of Ru3(CO)12, mono- and bidentate ligands and hydride acceptors was performed to enable dehydrogenation of primary alcohols to stop at the aldehyde stage. Among many H-acceptors screened, diphenylacetylene (tolane) proved the most suitable judged from its smooth reduction. Electron rich and deficient analogues of tolane have been synthesized and, based on competition experiments between these H-acceptors, a tentative catalytic cycle for the Ru3(CO)12/PPh3-catalyzed dehydrogenations has been proposed. 相似文献