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   642篇
  免费   16篇
化学   573篇
晶体学   4篇
力学   2篇
数学   7篇
物理学   72篇
  2023年   2篇
  2022年   3篇
  2021年   4篇
  2020年   6篇
  2019年   2篇
  2018年   5篇
  2016年   6篇
  2015年   9篇
  2014年   9篇
  2013年   23篇
  2012年   31篇
  2011年   28篇
  2010年   16篇
  2009年   18篇
  2008年   39篇
  2007年   29篇
  2006年   26篇
  2005年   42篇
  2004年   33篇
  2003年   29篇
  2002年   39篇
  2001年   14篇
  2000年   64篇
  1999年   27篇
  1998年   17篇
  1997年   15篇
  1996年   8篇
  1995年   6篇
  1994年   7篇
  1993年   12篇
  1992年   9篇
  1991年   7篇
  1990年   9篇
  1989年   5篇
  1988年   5篇
  1987年   7篇
  1986年   2篇
  1985年   8篇
  1984年   12篇
  1983年   5篇
  1982年   2篇
  1981年   4篇
  1980年   2篇
  1979年   4篇
  1978年   1篇
  1977年   3篇
  1976年   3篇
  1967年   1篇
排序方式: 共有658条查询结果,搜索用时 78 毫秒
31.
As advanced negative electrodes for powerful and useful high‐voltage bipolar batteries, an intercalated metal–organic framework (iMOF), 2,6‐naphthalene dicarboxylate dilithium, is described which has an organic‐inorganic layered structure of π‐stacked naphthalene and tetrahedral LiO4 units. The material shows a reversible two‐electron‐transfer Li intercalation at a flat potential of 0.8 V with a small polarization. Detailed crystal structure analysis during Li intercalation shows the layered framework to be maintained and its volume change is only 0.33 %. The material possesses two‐dimensional pathways for efficient electron and Li+ transport formed by Li‐doped naphthalene packing and tetrahedral LiO3C network. A cell with a high potential operating LiNi0.5Mn1.5O4 spinel positive and the proposed negative electrodes exhibited favorable cycle performance (96 % capacity retention after 100 cycles), high specific energy (300 Wh kg?1), and high specific power (5 kW kg?1). An 8 V bipolar cell was also constructed by connecting only two cells in series.  相似文献   
32.
Experiments were carried out to investigate the removals of SO2 and NOx from simulated lignite-burning flue gas containing SO2 (4800 ppm), NO (320 ppm) and H2O (22%) by electron beam irradiation. Removal efficiencies of SO2 and NOx were achieved to reach 97 and 88% at 70°C, and 74 and 85% at 80°C, respectively, with the dose of 10.3 kGy without NH3 leakage. The higher removal efficiencies of SO2 and NOx were observed in simulated lignite-burning flue gas than in coal-fired flue gas containing 800 ppm of SO2, 225 ppm of NO and 7.5% H2O at the same treatment condition. The higher removal efficiencies were attributed to the higher concentrations of SO2, H2O, and added NH3. Simulation calculations indicated that the higher concentrations of these components enhance the effective radical reactions to oxidize NO to form NO2 with HO2 radical, and to oxidize SO2 to form SO3 with OH radical and O2. The reactions of NOx with N and NH2 radicals to produce N2 and N2O also promote the NOx removal. By-product was determined to be the mixture of (NH4)2SO4 and NH4NO3 containing a small amount of H2SO4.  相似文献   
33.
A new ent-kaurane diterpene glycoside, beta-D-glucopyranosyl 17-hydroxy-ent-kauran-19-oate-16-O-beta-D-glucopyranoside (4) was isolated from the dried leaves of Cussonia bojeri SEEM., together with four known compounds identified as 16beta,17-dihydroxy-kauran-19-oic acid (1), beta-D-glucopyranosyl 16beta,17-dihydroxy-(-)-kauran-19-oate (2), paniculoside IV (3), and rutin (5). The structure of 4 was deduced on the basis of chemical and spectroscopic evidence.  相似文献   
34.
To develop a sensitive and selective chemiluminometric method for the determination of methylglyoxal, we used 2-aminonicotinic acid as the chemiluminescence derivatization reagent. 2-Aminonicotinic acid reacts with methylglyoxal in an acidic solution at 37 degrees C for 4 h and gave a chemiluminescence in N,N'-dimethylformamide containing sodium tert-butoxide. The detection limit (blank intensity plus three-times its standard deviation of methylglyoxal) for methylglyoxal is 233 fmol in the reaction mixture.  相似文献   
35.
Two sterically hindered tris-pyridyl methane ligands, tris(6-methyl-2-pyridyl)methane (L1) and bis(6-methyl-2-pyridyl)pyridylmethane (L2), are newly synthesized. Under aerobic conditions, Ln (n = 1 or 2) reacts with CuX2 (X = Cl or Br), oxygenated at the methine position to LnOH or LnOMe. The former alcoholate ligand creates trinuclear Cu(II) complexes [Cu3(X)(LnO)3](PF6)2 [(X, n) = (Br, 1) 1, (C1, 1) 2, (Br, 2) 3, or (C1, 2) 4] in which the alkoxide oxygen atoms bridge copper centers. The crystal structures of 1-4 are presented along with their magnetic susceptibility data. The weak antiferromagnetic coupling between the Cu(II) centers in this trinuclear arrangement is due to weak interaction of the magnetic orbitals (dz2) which are oriented along three alternate sides in a hexagon of the Cu3O3 core in 1-4. Under anaerobic conditions, L1 reacts with CuBr2 to form a square pyramidal complex [CuL1Br2] (9) with the ligand facially capping. [Cu(Br)2(L1OMe)] (10) was obtained after the suspension of 9 in MeOH was stirred under air for 48 h. In the presence of cyclohexene, 9 is converted to [Cu(Br)(L1)]m (m = 1 or 2) 5 quantitatively to give trans- 1,2-dibromocyclohexane, indicating that Br2 is generated during the reaction. The FAB MS spectrum of [18O]-1 prepared by the reaction of L1 with CuBr2 under 18O2 shows that the ligand of [18O]-1 is L1(18O-.) L1(18OH), L1OCD3, and bis(6-methyl-2-pyridyl) ketone were obtained from reaction of L1 with CuBr2 in CD3OD under 18O2. These results indicate that the origins of the O atom in L1OH and L1OMe are O2 and MeOH, respectively. On the basis of these results, a mechanism of the oxygenation of L1 in the present system will be proposed.  相似文献   
36.
37.
Shiga T  Ohba M  Okawa H 《Inorganic chemistry》2004,43(14):4435-4446
A series of trinuclear Cu(II)Ln(III)Cu(II) complexes with the bridging ligand 2,6-di(acetoacetyl)pyridine have been prepared by one-pot reaction with Cu(NO(3))(2).3H(2)O and Ln(NO(3))(3).nH(2)O in methanol. X-ray crystallographic studies for all the complexes indicate that two L(2)(-) ligands selectively sandwich two Cu(II) ions with the 1,3-diketonate entities and one Ln(III) ion with the 2,6-acetylpyridine entity to form a trinuclear CuLnCu core bridged by the enolate oxygen atoms. Cryomagnetic properties of the complexes are studied with respect to the electronic structure of the Ln ion.  相似文献   
38.
Green oxidation with aqueous hydrogen peroxide   总被引:2,自引:0,他引:2  
Aqueous H2O2 is an ideal oxidant, when coupled with a tungstate complex and a quaternary ammonium hydrogensulfate as an acidic phase-transfer catalyst. It oxidizes alcohols, olefins, and sulfides under organic solvent- and halide-free conditions in an economically, technically, and environmentally satisfying manner.  相似文献   
39.
40.
In the title compound, trans‐[CoCl(NO2)(C2H8N2)2]NO3, a distorted octahedral CoIII complex shows an orientational disorder such that the positions of the nitro and chloro ligands are exchanged. The occupation factors of the major and minor orientations are 84 and 16%, respectively. The O atoms of the nitrate ion are disordered over two sites.  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