全文获取类型
收费全文 | 11866篇 |
免费 | 1845篇 |
国内免费 | 1794篇 |
专业分类
化学 | 12798篇 |
晶体学 | 543篇 |
力学 | 67篇 |
综合类 | 54篇 |
数学 | 111篇 |
物理学 | 1932篇 |
出版年
2024年 | 31篇 |
2023年 | 227篇 |
2022年 | 280篇 |
2021年 | 339篇 |
2020年 | 539篇 |
2019年 | 462篇 |
2018年 | 309篇 |
2017年 | 439篇 |
2016年 | 585篇 |
2015年 | 570篇 |
2014年 | 618篇 |
2013年 | 887篇 |
2012年 | 815篇 |
2011年 | 889篇 |
2010年 | 688篇 |
2009年 | 782篇 |
2008年 | 822篇 |
2007年 | 873篇 |
2006年 | 708篇 |
2005年 | 669篇 |
2004年 | 706篇 |
2003年 | 622篇 |
2002年 | 449篇 |
2001年 | 328篇 |
2000年 | 258篇 |
1999年 | 269篇 |
1998年 | 226篇 |
1997年 | 173篇 |
1996年 | 154篇 |
1995年 | 170篇 |
1994年 | 94篇 |
1993年 | 67篇 |
1992年 | 70篇 |
1991年 | 46篇 |
1990年 | 38篇 |
1989年 | 22篇 |
1988年 | 21篇 |
1987年 | 17篇 |
1986年 | 21篇 |
1985年 | 21篇 |
1983年 | 13篇 |
1982年 | 17篇 |
1981年 | 18篇 |
1980年 | 14篇 |
1979年 | 18篇 |
1978年 | 15篇 |
1976年 | 12篇 |
1975年 | 16篇 |
1974年 | 15篇 |
1971年 | 17篇 |
排序方式: 共有10000条查询结果,搜索用时 59 毫秒
111.
On a New Copper Cobalt Borate Oxide with Isolated B2O5 Units: Cu2Co(B2O5)O Single crystals of a new compound with the empirical formula Cu2CoB2O6 were obtained by using a B2O3 flux technique. X-ray single crystal technique led to a new structure type. Cu2CoB2O6 crystallizes monoclinic, space group C-P21/c (No. 14); a = 3.2250(6); b = 14.847(1); c = 9.1171(6) Å; β = 93.67°; Z = 4. All metal sites are octahedrally coordinated and form a two dimensional framework consisting of edge sharing octahedra ribbons. In addition one observes isolated B2O5-units and oxygen which is not coordinated to boron. The far relation to the crystal structure of the mineral Warwickite is illustrated. 相似文献
112.
113.
Brunner H Cattey H Meier W Mugnier Y Stückl AC Wachter J Wanninger R Zabel M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(16):3796-3802
The reaction of the cluster salts [Cp(2*) Nb(CO)(2)](n)[Co(11)Te(7)(CO)(10)] (Cp*=C(5)Me(5); n=1, 2) with excess PMe(2)Ph gave the neutral, dark brown clusters [Co(11)Te(7)(CO)(6)(PMe(2)Ph)(4)] (5) and [Co(11)Te(7)(CO)(5)(PMe(2)Ph)(5)] (6) with 147 metal valence electrons. The new compounds were characterized by IR spectroscopy, elemental analyses, and mass spectrometry. The molecular structure of 6 was determined by X-ray crystallography. Like its precursor anion, it consists of a pentagonal-prismatic [Co(11)Te(7)] core, but with a ligand sphere composed of five CO and five PMe(2)Ph ligands. Detailed electrochemical studies of both reactions reveal that a stepwise substitution of CO ligands in the initial cluster anions takes place leading to intermediate [Co(11)Te(7)(CO)(10-m)(PMe(2)Ph)(m)](n-) ions (m=1-5; n=1, 2). Each of these intermediates is distinguished by at least one oxidation and two reduction waves, giving rise to a total of 21 redox couples and 27 electroactive species. The electron sponge character of the new compounds is particularly pronounced in 5, which exhibits charges n between +1 and -4 corresponding to metal valence electron counts of between 146 and 151. 相似文献
114.
Fedushkin IL Morozov AG Rassadin OV Fukin GK 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(19):5749-5757
Compounds [Sr(dpp-bian)(thf)4] (2), [Ba(dpp-bian)(dme)2.5] (3) and [Mg(dtb-bian)(thf)2] (4) (dpp-bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene; dtb-bian = 1,2-bis[(2,5-di-tert-butylphenyl)imino]acenaphthene) were prepared by reduction of dpp-bian and dtb-bian with an excess of metallic Mg, Sr, or Ba in THF or DME. Reactions of [Mg(dpp-bian)(thf)3], 3, and 4 with diphenylacetonitrile gave keteniminates [Mg(dpp-bianH)(NCCPh2)(thf)2] (5), [Mg(dtb-bianH)(NCCPh2)(thf)2] (6), and [Ba(dpp-bianH)(NCCPh2)(dme)2] (7), respectively. The reaction of 2 with CH3C[triple chemical bond]N in THF gave [{Sr(dpp-bianH)[N(H)C(CH3)C(H)CN](thf)}2] (8). The compounds 2, 3, 5-8 were characterized by elemental analysis, and IR and NMR spectroscopy. Molecular structures of 2, 3, 7, and 8 were determined by single-crystal X-ray diffraction. In contrast to reactions of alkali-metal reagents, magnesium amides, or yttriumalkyls with alpha-H acidic nitriles, which are accompanied by an amine or an alkane elimination, the reactions of [Mg(dpp-bian)(thf)3] (1), 2, 3, and 4 with such nitriles proceeded with formation of Mg, Sr, and Ba keteniminates and simultaneous protonation of one nitrogen atom of the bian ligand. The NMR spectroscopic data obtained for complex 5 indicated that in solution the amino hydrogen atom underwent the fast (on the NMR timescale) shuttle transfer between both nitrogen atoms of the dpp-bianH ligand. 相似文献
115.
The texture of Cr2O3-K2O/Al2O3catalysts containing oxides of rare earth elements (REE) was studied. The catalysts are used for the synthesis of 2-methylthiophene by the reaction of H2S with n-pentane or piperilene. The heterocyclization of n-pentane is a consecutive reaction involving a step of dehydrogenation of initial hydrocarbon. At this step the texture of the catalyst affects the yield of 2-methylthiophene. The yield of 2-methylthiophene obtained from piperilene and I2S is independent of the catalyst texture. 相似文献
116.
Enantiomerically pure iridium complexes with phosphino‐ and (phosphinooxy)‐substituted N‐heterocyclic carbene (NHC) ligands were synthesized. Investigation of their electronic properties showed a similar trans influence of the phosphino (or phosphinooxy) and the NHC units. The complexes were tested in iridium‐catalyzed hydrogenation. While low conversions were observed with unfunctionalized olefins, the catalysts proved to be suitable for hydrogenation of the α,β‐unsaturated ester 20 , allylic alcohol 21 , and imine 22 . The enantioselectivities were, however, moderate. 相似文献
117.
118.
考察了在离子液体1-正丁基-3-甲基咪唑四氟硼酸盐([bmim][BF4])介质中, 芳香醛与5,5-二甲基-1,3-环己二酮的缩合反应. 实验结果表明, 在催化量的FeCl3•6H2O存在下, 该反应可高产率地生成氧杂蒽二酮类化合物3; 而在TMSCl/FeCl3•6H2O复合催化体系的催化下, 则得到氧杂蒽二酮类化合物的开环衍生物4, 反应具有非常好的选择性. 该论文提供的方法操作简单、产率高、选择性好而且对环境友好. 在反应结束后, 所用催化剂及离子液体都很容易回收, 并能有效重复使用. 相似文献
119.
Nusbaumer H Zakeeruddin SM Moser JE Grätzel M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(16):3756-3763
A series of new cobalt complexes [Co(LLL)(2)X(2)] were synthesized and evaluated as redox mediators for dye-sensitized nanocrystalline TiO(2) solar cells. The structure of the ligand and the nature of the counterions were found to influence the photovoltaic performance. The one-electron-transfer redox mediator [Co(dbbip)(2)](ClO(4))(2) (dbbip = 2,6-bis(1'-butylbenzimidazol-2'-yl)pyridine) performed best among the compounds investigated. Photovoltaic cells incorporating this redox mediator yielded incident photon-to-current conversion efficiencies (IPCE) of up to 80%. The overall yield of light-to-electric power conversion reached 8 % under simulated AM1.5 sunlight at 100 W m(-2) intensity and more than 4% at 1000 W m(-2). Photoelectrodes coated with a 2 microm thick nanoporous layer and a 4 microm thick light-scattering layer, sensitized with a hydrophobic ruthenium dye, gave the best results. 相似文献
120.
氧化共沉淀法制备纳米级掺锑α—Fe2O3气敏陶瓷粉料 总被引:1,自引:0,他引:1
氧化共沉淀法制备纳米级掺锑α┐Fe2O3气敏陶瓷粉料王忠春**刘尔生陈耐生*黄金陵(福州大学化学系福州350002)关键词α-Fe2O3陶瓷,锑掺杂气敏材料,纳米材料1996-10-05收稿,1997-04-22修回福建省科委资助项目**现在上海硅酸... 相似文献