首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   7625篇
  免费   1013篇
  国内免费   2102篇
化学   9804篇
晶体学   33篇
力学   52篇
综合类   59篇
数学   7篇
物理学   785篇
  2024年   14篇
  2023年   126篇
  2022年   254篇
  2021年   338篇
  2020年   430篇
  2019年   328篇
  2018年   303篇
  2017年   283篇
  2016年   390篇
  2015年   388篇
  2014年   488篇
  2013年   806篇
  2012年   523篇
  2011年   491篇
  2010年   434篇
  2009年   432篇
  2008年   517篇
  2007年   542篇
  2006年   462篇
  2005年   408篇
  2004年   410篇
  2003年   446篇
  2002年   360篇
  2001年   226篇
  2000年   214篇
  1999年   177篇
  1998年   137篇
  1997年   150篇
  1996年   137篇
  1995年   118篇
  1994年   94篇
  1993年   70篇
  1992年   69篇
  1991年   41篇
  1990年   41篇
  1989年   25篇
  1988年   19篇
  1987年   10篇
  1986年   8篇
  1985年   11篇
  1984年   6篇
  1983年   4篇
  1982年   1篇
  1981年   3篇
  1980年   2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
91.
Side self-oxidation of thiols was studied. It was found that these reactions in neutral and alkaline solutions are induced by impurities of variable-valence metals. The ability of transition metals to catalyze oxidation of thiols changes in the order Cu > Mn > Fe > Ni Co. The plot of the self-oxidation rate vs. pH passes through a maximum whose position on the pH scale depends on both the nature of metal and the structure of the thiol oxidized. For thiols having different structures, the kinetic orders in reactions catalyzed by copper ions differently vary with pH, which is apparently associated with the formation of complexes possessing different catalytic activity.  相似文献   
92.
Cs-Fe-Co-Bi-Mn-Mo复合氧化物选择性催化氧化异丁烯   总被引:2,自引:0,他引:2  
Mixed oxide catalyst Cs0.1 Fe2Co6BiMnMo12 Ox was prepared by the interprecipitation method, then the catalyst was calcined at different temperature. Selective oxidation of isobutene was carried out in a fixed-bed reactor. The results showed that the catalyst has high catalytic activity. Under the optimum reaction conditions ( n(-C4^= ) : n(O2) = 1:2-1:4, space velocity = 180h^-1, T = 360℃ ), the yield of methacmlein and methacrylic reached 80%, 8 %,respectively. The total yields of liquid products( methacrolein, methacrylic acid and acetic acid) reached about 90%.  相似文献   
93.
A novel diselenide was synthesized in good yield via only four steps from phenol, and was employed as the catalyst for the Baeyer-Villiger oxidation with 30% H2O2 to obtain lactones in good yields.  相似文献   
94.
The polystyrene supported glutamic acid Schiff base complex of Mn ( Ⅱ ) (PS-Sal-Glue-Mn) was prepared with chloromethylated styrene polymer beads, 2,4-dihydroxybenzaldehyde, L-glutamic acid and manganese ( Ⅱ ) acetate tetrahyrate. The polymeric ligand and the complex were characterized by FT-IR, small area X-ray photoelectron spectroscopy (XPS) and 1CP-AES. In the presence of the manganese complex, cyclohexene (1) was effectively oxidized by molecular oxygen without reductant. The major products of the reaction were 2-cyclohexen-l-ol (2), 2-cyclohexen-l-one (3) and 2-cyclohexen-1- hydroperoxide (4), which was different with typical oxidation of cyclohexene. The influence of reaction temperature and additive for oxidation had been studied. The selectivity of 2-cyclohexen-1-hydroperoxide varied with reaction time and different additives. The mechanism of cyclohexene oxidation had also been discussed.  相似文献   
95.
 采用恒电流电解法,在1-丁基-3-甲基咪唑硫酸氢盐([bmim]HSO4)离子液体中合成了苯胺与环氧丙烷共聚物(PAN-PPO). 扫描电镜观察表明, PAN-PPO由直径小于80 nm的纳米纤维组成. PAN-PPO对草酸氧化具有较好的电催化活性. 采用电化学原位红外光谱技术对草酸的电催化氧化进行了简单的分析.  相似文献   
96.
In this study a relationship between the surface and textural properties of carbon blacks and the gasification process induced thermally in air is noted. A temperature jump method was used to follow the gasification in air and to establish the relevant Arrhenius parameters. This can be associated with the activity of ‘basal’ plane carbon atoms as well as ‘edge’ carbon atoms at the surface. This is based on a model of carbon black structure consisting of the irregular packing of small graphite carbon structures. The carbon black surface was measured using a single measurement of adsorption based essentially on the BET volumetric method. The carbon black surface had a rate of oxidation per unit are which clearly indicated that the lower area carbon blacks had a predominately active area of ‘edge’ atoms at the surface while the surface of the higher area carbon blacks had a predominate amount of ‘basal’ plane graphite carbon atoms.  相似文献   
97.
选择性氧化含氰基的对硝基苯硫醚   总被引:2,自引:0,他引:2  
选择性氧化含氰基的对硝基苯硫醚岳国仁,王建华,张正(南京大学化学系南京210008)关键词含氰基硫醚,选择性氧化,四水合过硼酸钠据报道[1]对硝基苯磺酰基乙腈的合成,反应时间长,可采用四水合过硼酸钠(NaBO3·4H2O)作为氧化剂,受到重视[2,3...  相似文献   
98.
油莱甾醇内酯(Brassinolide)(1)是一种高效的植物生长激素,其生理活性与侧链中C_(22)、C_(23)的构型密切相关。当C_(22)、C_(23)为S、S构型时,其活性仅为1的十分之一。在1的  相似文献   
99.
采用电沉积-热解法在3Cr25Ni7N合金表面制备了Y2O3薄膜,并研究了薄膜处理对合金在1000℃空气中的抗高温氧化性能的影响。氧化动力学曲线、SEM及XRD分析结果表明,Y2O3薄膜处理使合金表面氧化膜以尖晶石结构为主,氧化膜致密,有效地抑制了Cr2O3的挥发反应,且氧化膜与基体的附着性好,因此合金在高温下的抗氧化性能得到提高,这与氧化钇薄膜在较低温度下抗高温氧化性能提高的机制是不同的。在不同温度下,Y2O3薄膜处理均可以有效提高合金的抗高温氧化性能。  相似文献   
100.
The gas-phase photocatalytic oxidation of aniline on a new kind of porous nano-TiO2 composite films is investigated. The composite film was prepared on glass fiber with the water glass as binders and dilute H2SO4 solution as solidifying reagent. The surface characters were observed by scanning electron microscope. The photocatalytic degradation of aniline on the composite films was carried out in a TiO2/UV system. Some important factors affecting the photodegradation, such as the concentration of TiO2, the initial concentration of aniline, and the existing water vapor, are also studied. The product of photocatalytic oxidation was detected by Fourier transform-Infrared. The partial intermediate products were absorbed on TiO2 surface, which resulted in catalyst deactivation. But when it was irradiated under UV illumination or solar irradiation for some time, the catalyst could be reused without loss of catalytic activity. Translated from the Journal of Wuhan University (Natural Science Edition), 2005, 51(2) (in Chinese)  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号