全文获取类型
收费全文 | 7950篇 |
免费 | 873篇 |
国内免费 | 2225篇 |
专业分类
化学 | 10071篇 |
晶体学 | 33篇 |
力学 | 53篇 |
综合类 | 61篇 |
数学 | 7篇 |
物理学 | 823篇 |
出版年
2024年 | 23篇 |
2023年 | 134篇 |
2022年 | 252篇 |
2021年 | 335篇 |
2020年 | 417篇 |
2019年 | 322篇 |
2018年 | 301篇 |
2017年 | 280篇 |
2016年 | 385篇 |
2015年 | 390篇 |
2014年 | 485篇 |
2013年 | 819篇 |
2012年 | 532篇 |
2011年 | 492篇 |
2010年 | 445篇 |
2009年 | 451篇 |
2008年 | 536篇 |
2007年 | 564篇 |
2006年 | 486篇 |
2005年 | 420篇 |
2004年 | 420篇 |
2003年 | 451篇 |
2002年 | 383篇 |
2001年 | 247篇 |
2000年 | 246篇 |
1999年 | 190篇 |
1998年 | 154篇 |
1997年 | 162篇 |
1996年 | 146篇 |
1995年 | 128篇 |
1994年 | 102篇 |
1993年 | 78篇 |
1992年 | 74篇 |
1991年 | 45篇 |
1990年 | 44篇 |
1989年 | 34篇 |
1988年 | 20篇 |
1987年 | 15篇 |
1986年 | 7篇 |
1985年 | 11篇 |
1984年 | 6篇 |
1983年 | 3篇 |
1982年 | 3篇 |
1981年 | 3篇 |
1980年 | 3篇 |
1977年 | 1篇 |
1973年 | 1篇 |
1969年 | 1篇 |
1959年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
111.
Half-wave potentials of the one-electron electrochemical oxidation (E
1/2
ox) of hydroquinolines with different degrees of heterocycle hydrogenization as well as containing substituents of various natures in the benzene ring and heterocycle have been measured. Linear correlations betweenE
1/2
ox and the values of the Hammett polar -constants form- andp-substituents in dihydroquinolines and related sulfur-containing dithiolthiones were established. The character of the variation ofE
1/2
ox in the series of hydroquinolines was found to correlate with the characteristic features of the inhibiting action of these compounds in the liquid-phase oxidation of various hydrocarbons. However, in contrast to phenolic antioxidants for hydroquinolines, there is no dependence of the retardation period onE
1/2
oxin the oxidation of hydrocarbons at temperatures higher than 100 °C.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 610–613, April, 1994. 相似文献
112.
Soot deep oxidation catalyzed by molybdena and molybdates: a thermogravimetric investigation 总被引:2,自引:0,他引:2
Molybdena (MoO3) and molybdates of bismuth (Bi2Mo3O12), chromium (Cr2Mo3O12), barium (BaMoO4), manganese (MnMoO4) and copper (Cu3Mo2O9) were synthesized and characterized by X-ray powder diffractometry and infrared spectroscopy. They were then assessed as ‘loose contact' catalysts for soot deep oxidation (combustion) in air by thermogravimetry. A similar assessment was carried out on commercial chromia (Cr2O3) and tungsta (WO3). Observed high oxidation activity of MoO3, as compared to both Cr2O3 and WO3, is attributed to the higher volatility (mobility) of MoOx species. On similar grounds, observed high activity of MoO3 and Cu3Mo2O9, as compared to the other test molybdates, is explained. Relatively speaking, however, a higher activity was observed for Cu3Mo2O9 than MoO3, whereby soot ignition temperature decreased from 571°C (uncatalyzed oxidation) to 430°C, to occur within the temperature range of diesel exhaust (200–450°C). This observation is ascribed to copper-promoted redox conduct of Mo(VI) in the oxidation reaction of soot. Kinetics of the reaction was studied non-isothermally, and the kinetic parameters (A, k, ΔE and the reaction order) were calculated. 相似文献
113.
WANG Gui-Xiu ZHU Rong-Xiu ZHANG Dong-Ju② LIU Cheng-Bu 《结构化学》2006,25(11):1402-1408
1 INTRODUCTION Ethers are a kind of organic compounds that are easily oxidized under the conditions of lacking light and any additional excitement. According to dif- ferent mechanisms, the oxidation reactions could be classified into two types: photooxidation reaction and dark oxidation reaction. The former is the reaction with excited state oxygen molecule (singlet state), while the latter is the reaction with ground state oxygen molecule (triple state) without illuminance or any exciter… 相似文献
114.
C. V. Rode M. M. Telkar R. Jaganathan R. V. Chaudhari 《Journal of molecular catalysis. A, Chemical》2003,200(1-2):279-290
Liquid phase hydrogenation of styrene oxide using 1% Pd/C and NaOH as a promoter was found to give selectively β-phenethyl alcohol (PEA) under very mild conditions (313–333 K; 0.68–5.5 MPa). The kinetics of this system was investigated by collecting initial rate data in a batch slurry reactor. Rate of hydrogenation was found to decrease beyond a certain concentration of both hydrogen (>3 MPa) and styrene oxide (>0.5 kmol/m3). A Langmuir–Hinshelwood type rate equation has been proposed based on the initial rate data in the kinetic regime. The model predictions agree very well with the experimentally observed concentration–time data indicating the applicability of the proposed rate model. 相似文献
115.
QijianZhang DehuaHe QimingZhu 《天然气化学杂志》2003,12(2):81-89
The direct conversion of methane to methanol has attracted a great deal of attention for nearly a century since it was first found possible in 1902, and it is still a challenging task. This review article describes recent advancements in the direct partial oxidation of methane to methanol. The history of direct oxidation of methane and the difficulties encountered in the partial oxidation of methane to methanol are briefly summarized. Recently reported developments in gas-phase homogeneous oxidation, heterogeneous catalytic oxidation and liquid phase homogeneous catalytic oxidation of methane axe reviewed. 相似文献
116.
The structure of the strongly cytotoxic marine alkaloid halitulin (1) has been confirmed by total synthesis and its absolute configuration determined as (15S). The synthesis follows a strategy previously reported by one of us and uses an efficient preparation of the quinoline-7,8-diol unit by modified Baeyer-Villiger and Skraup reactions. The O-benzyl protecting groups were removed in the last step of the synthesis by transfer hydrogenolysis without concomitant reduction of the quinoline ring. The method can be applied for the synthesis of halitulin analogues. 相似文献
117.
LaSrBO4(B=Cu、Ni、 Co、 Fe、 Mn、 Cr ) was studied with respect to their preparation, characteristics and catalytic oxidation activity by means of XRD, XPS, electric conductivity and activity evaluation. Results showed that the calcination temperature has great influence on the formation of the phases of such samples, and was associated with the radius of B ion. The greater the B ion radius, the higher the calcination temperature required for the formation of the phases. It was also found that the activity and the relative content of adsorptive oxygen and lattice oxygen on the sample surf are, the activation energy of electron conduction and the CO oxidation activity may vary with different B ions, and demonstrate a dual-peak pattern with the increase in the number of 3d electrons of the B ion. 相似文献
118.
A. R. Burilov D. V. Cherepachkin I. L. Nikolaeva M. A. Pudovik 《Russian Chemical Bulletin》1995,44(2):345-349
Some newS-phosphorylated,S-silylated, andS-stannylated derivatives of -mercaptoketones were obtained. The reactions of some of these compounds induced by the temperature and by molecular oxygen as well as the phosphorylation of the Si- and Sn-containing derivatives were studied.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 353–357, February, 1995. 相似文献
119.
E. V. Gorobetz A. N. Kasatkin A. V. Kutchin G. A. Tolstikov 《Russian Chemical Bulletin》1994,43(3):466-470
Hydroalumination of methyl nopol ether with a LiAlH4-3AlBr3 system is accompanied by a skeleton rearrangement and gives 6-dibromoalumo-7-methoxymethyl-2-menthene. Further hydroalumination affords a mixture of 2,6- and 2,5-bis(dibromoalumo)-7-(methoxymethyl)menthanes in 8020 ratio. Hydrolysis and oxidation of these organoaluminum compounds were carried out.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 506–510, March, 1994. 相似文献
120.
We assess several models for the environment of the P
b
center (Si dangling bond center) at the interface of Si(111) with its oxide. The comparison of hyperfine constants observed with those predicted using large cluster models favors a local structure in which there is an Si-Si bond within the oxide close to the Si dangling bond. Such Si-Si bonds are also suggested by a number of other experiments and are consistent with the reactive layer model proposed to rationalize a range of oxidation studies. 相似文献