全文获取类型
收费全文 | 740篇 |
免费 | 137篇 |
国内免费 | 233篇 |
专业分类
化学 | 1076篇 |
力学 | 1篇 |
综合类 | 1篇 |
物理学 | 32篇 |
出版年
2024年 | 4篇 |
2023年 | 14篇 |
2022年 | 24篇 |
2021年 | 28篇 |
2020年 | 50篇 |
2019年 | 34篇 |
2018年 | 38篇 |
2017年 | 35篇 |
2016年 | 30篇 |
2015年 | 40篇 |
2014年 | 58篇 |
2013年 | 56篇 |
2012年 | 47篇 |
2011年 | 47篇 |
2010年 | 37篇 |
2009年 | 32篇 |
2008年 | 40篇 |
2007年 | 31篇 |
2006年 | 26篇 |
2005年 | 26篇 |
2004年 | 27篇 |
2003年 | 32篇 |
2002年 | 157篇 |
2001年 | 33篇 |
2000年 | 21篇 |
1999年 | 26篇 |
1998年 | 26篇 |
1997年 | 18篇 |
1996年 | 16篇 |
1995年 | 12篇 |
1994年 | 11篇 |
1993年 | 9篇 |
1992年 | 9篇 |
1991年 | 3篇 |
1990年 | 5篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1987年 | 1篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1982年 | 2篇 |
排序方式: 共有1110条查询结果,搜索用时 15 毫秒
21.
22.
L. M. Pisarenko T. V. Maksimova Z. S. Kartasheva O. T. Kasaikina 《Russian Chemical Bulletin》2003,52(7):1500-1503
The temperature effect on the rate of the decomposition of hydroperoxides and the rate of the formation of free radicals in the oxidation of ethylbenzene with molecular oxygen in the presence of -phenylethyl hydroperoxide—cetyltrimethylammonium bromide (CTAB) as a catalytic system for free radical generation was studied by kinetic methods (from the oxygen consumption and hydroperoxide decomposition rates) and the inhibition method involving different acceptors of free radicals. 相似文献
23.
24.
Narcís Homs Jordi Llorca Montserrat Riera Jordi Jolis Jos-Luis G. Fierro Joaquim Sales Pilar Ramírez de la Piscina 《Journal of molecular catalysis. A, Chemical》2003,200(1-2):251-259
Silica-supported trimetallic catalysts containing Pt, Sn and a group 13 metal (PtSnM, M=Ga, In, Tl) were prepared by consecutive impregnation steps from cis-[PtCl2(PPh3)2] and chloride precursors. X-ray diffraction (XRD), transmission electron microscopy (TEM), selected-area electron diffraction (ED) and energy dispersive X-ray analysis (EDX) showed large platelet-like particles of PtSn1−xMx phases. PtSnGa catalyst with a Pt/(Sn+Ga) molar ratio of 1.72 showed a bimodal particle distribution and a Pt phase was identified. Differences in surface structures were also revealed by the performance of catalysts in the dehydrogenation of n-hexane. For PtSnIn and PtSnTl (Pt/(Sn+M) molar ratio of about 1) the dehydrogenation was favoured. In contrast, PtSnGa catalyst yielded hydrogenolysis products. Photoelectron spectra showed the Pt 4f7/2 level at a binding energy of 70.0–71.8 eV in all cases. Moreover, the FT-IR spectra of chemisorbed CO on the PtSnGa showed a slight shift in the ν(CO) toward higher values with respect to the monometallic catalyst, pointing to an electronic effect in accordance with photoelectron spectroscopy. 相似文献
25.
In the research the various ways of increasing the selectivity of the dehydrogenation process and reducing the intensity of coke formation have been studied. All results were received by means of the mathematical model of the dehydrogenation process with the calculating technique of optimal water flow. The main conclusion consists in the fact that the decrease in molar ratio H2/feed leads to increasing the catalyst deactivation by coke. It can be partially compensated by increasing the supplied water flow to the reactor to 13-14 l/h instead of 9-10 l/h at the end of cycle. Reducing the life of the catalyst to 270-290 days even at an increased water flow is determined by the intensity of the coking reactions. However, the economic feasibility of operating in such condition causes a considerable increase in production of LAB to 181-186 t/day. 相似文献
26.
27.
28.
Silver nanoparticles immobilized onto poly(4‐vinylpyridine)‐functionalized magnetic nanoparticles: A robust magnetically recyclable catalyst for oxidant‐free alcohol dehydrogenation 下载免费PDF全文
A heterogeneous and recyclable catalyst with a high loading of silver nanoparticles was synthesized via the silver nanoparticles being supported onto the surface of magnetic nanoparticles coated with poly(4‐vinylpyridine). The synthesized catalyst was used in the dehydrogenation of alcohols to corresponding carbonyl compounds. A broad diversity of alcohols was converted into their corresponding carbonyl compounds in excellent yields. The catalyst was easily recovered by applying an external magnetic field and reused for seven reaction cycles without considerable loss of activity. The catalyst was fully characterized using various techniques. 相似文献
29.
30.
Mechanistic investigation of imine formation in ruthenium‐catalyzed N‐alkylation of amines with alcohols 下载免费PDF全文
Imines are observed frequently in ruthenium‐catalyzed N‐alkylation of amines with alcohols. Herein, nitrogen–phosphine functionalized carbene ligands were developed and used in ruthenium‐catalyzed N‐alkylation to explore the mechanism of imine formation. The results showed that strongly electron‐donating ligands were beneficial for imine formation and alcohol dehydrogenation to generate acid. In addition, with an increase of electron density of nitrogen atom in substituted amines, the yield of imines in N‐alkylation was improved. At the same time, with electron‐rich imines as substrates, the transfer hydrogenation of imines became difficult. It is suggested that strongly electron‐donating ligands and substrates caused an increase of electron density on the ruthenium center, which resulted in the elimination of hydrogen atoms in active species [LRuH2] as hydrogen gas rather than transfer onto the imine coordinated with the ruthenium center. 相似文献