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   1469篇
  免费   169篇
  国内免费   595篇
化学   1879篇
晶体学   26篇
力学   39篇
综合类   15篇
数学   94篇
物理学   180篇
  2024年   27篇
  2023年   91篇
  2022年   221篇
  2021年   223篇
  2020年   220篇
  2019年   186篇
  2018年   105篇
  2017年   106篇
  2016年   104篇
  2015年   78篇
  2014年   117篇
  2013年   159篇
  2012年   97篇
  2011年   70篇
  2010年   48篇
  2009年   53篇
  2008年   57篇
  2007年   60篇
  2006年   44篇
  2005年   29篇
  2004年   31篇
  2003年   21篇
  2002年   11篇
  2001年   10篇
  2000年   15篇
  1999年   3篇
  1998年   2篇
  1997年   6篇
  1996年   8篇
  1995年   3篇
  1994年   4篇
  1993年   5篇
  1992年   3篇
  1991年   4篇
  1990年   2篇
  1989年   1篇
  1988年   1篇
  1987年   1篇
  1985年   2篇
  1984年   1篇
  1983年   1篇
  1981年   1篇
  1980年   1篇
  1977年   1篇
排序方式: 共有2233条查询结果,搜索用时 15 毫秒
1.
The design of new solid-state proton-conducting materials is a great challenge for chemistry and materials science. Herein, a new anionic porphyrinylphosphonate-based MOF ( IPCE-1Ni ), which involves dimethylammonium (DMA) cations for charge compensation, is reported. As a result of its unique structure, IPCE-1Ni exhibits one of the highest value of the proton conductivity among reported proton-conducting MOF materials based on porphyrins (1.55×10−3 S cm−1 at 75 °C and 80 % relative humidity).  相似文献   
2.
Palladium nanoparticle‐incorporated metal–organic framework MIL‐101 (Pd/MIL‐101) was successfully synthesized and characterized using X‐ray diffraction, nitrogen physisorption, X‐ray photoelectron, UV–visible and infrared spectroscopies, and transmission electron microscopy. The characterization techniques confirmed high porosity and high surface area of MIL‐101 and high stability of nano‐size palladium particles. Pd/MIL‐101 nanocomposite was investigated for the Sonogashira cross‐coupling reaction of aryl and heteroaryl bromides with various alkynes under copper‐free conditions. The reusability of the catalyst was tested for up to four cycles without any significant loss in catalytic activity. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   
3.
Guided by the self-penetrating features can improve the stability of metal organic frameworks (MOFs), an unprecedented 3D self-penetrated framework, {[Zn (tptc)0.5(bimb)]·H2O}n ( NUC-6 , here NUC corresponding to North University of China), with 3D (4,4)-c {86} net, was designed. Benefit from the high chemical stability and excellent luminescent property, NUC-6 can be act as an efficient multi-response chemo-sensor in detecting dichloronitroaniline pesticide and nitrofuran antibiotics in water with the detection limits are 116 ppb for DCN pesticide, 16 ppb for NFT antibiotic, and 12 ppb for NTZ antibiotic. Besides, the mechanisms of luminescence quenching were revealed from the viewpoint of internal filter effect (IFE) and photo-induced electron transfer (PET), implied by the optical spectroscopy and quantum chemical calculation. This work provides a promising strategy to design stable MOFs by improving the self-penetrating features and to expand their practical applications in the detection of organic pollutants in aqueous medium.  相似文献   
4.
IntroductionPolyoxometalatesarewidelystudiedfortheirin terestingapplicationsincatalysis ,electronicconduc tivity ,magnetism ,nonlinearopticsandmedicine[1— 4 ] .Whilethemechanismofthesynthesisofpolyoxometalatesremainselusiveandisoftende scribedasself assembly ,thereseemstobeanincreas inguseofthecombinationofthehydrothermalmethodandthestructure directingtemplate .There searchwiththismethodhasdemonstratedthatanum beroftransitionmetaloxides ,typicallyreducedmolybdenumoxides ,mixedvalancevanadiumo…  相似文献   
5.
用核磁共振对非晶态中B3+离子的微观结构进行了测定,结合Raman光谱的研究,对Li2O-B2O3-P2O5系统非晶态的性能(电导率、密度等)在P2O5/B2O3比约等于1时产生极值的原因从理论上作了阐明。  相似文献   
6.
The La(III) complex with a new amide‐type tripodal ligand,2,2′.2″‐nitrilotris{[(2′‐benzylaminofomyl)‐phenoxylethyl)amine (L), was synthesized and characterized by X‐ray crystallographic analysis. Crystal data: C48H55.50LaN7O18.75, Mr=1169.40, monoclinic. space group, P21/n, a= 1.0644(3) nm. b=2.3889(5) nm, c= 2.1917(5) nm, β=90.65°, V=5.573(2) nm3, Z=1, Dc=1.394 g°cm?3, R1=0.0487, wR [1>2s?(I)]=0.1266. The results reveal that each La(III) ion binds to 9 oxygen atoms, three of which belong to carbonyl groups from three tripodal ligands and six to three bidentate nitrate groups and a two‐dimensional sheet of 4.82 networks is assembled by metal‐ligand coordination interaction. L, a heptadentate compound, merely acts as a tridentate bridging spacer due to its steric hindrance and links the La(III) ions as three‐connected nodes.  相似文献   
7.
A novel 3D metal-organic coordination polymer Pb(1,4-napdc)(DMF) (1,4-napdc=naphthalene-1,4-dicarboxylate) was synthesized at room temperature using slow vapor diffusion method to grow single crystal that has been analyzed by X-ray diffraction. The crystal belongs to orthorhombic with space group P212121. The unit cell parameters are as fellows: a=0.701 3(2) nm, b=1.407 6(3) nm, c=1.521 5(4) nm, V=1.501 8(6) nm3 and Z=4. In the crystal structure of Pb(1,4-napdc)(DMF), the square grids constructed with paddle-wheel units of Pb(Ⅱ) and 1,4-napdc links stack over each other to generate infinite 3D network, which has square apertures (1.158×1.158 nm2) along the crystallographic a-axis. The thermal stability of compound was investigated by differential scanning calorimetry and thermogravimetric analysis. CCDC: 293617.  相似文献   
8.
Introduction In recent years,considerable attention has been paid to supramolecular networks based on metal organic building blocks because of their potential applications in diverse fields,such as,catalysis,optics,sensors, magnetism,and molecular recognition[1-3].On the ba-  相似文献   
9.
10.
陈文斌  李牛  项寿鹤 《中国化学》2005,23(3):255-260
本文报道了一种新型三维亚磷酸锌[HO(CH2)2NH3]2•[Zn3(HPO3)4]的合成和晶体结构。在它的结构中,ZnO4和HPO3严格按照顶点连接的方式交替相连。骨架结构存在两个沿着不同方向无限延伸的由ZnO4和HPO3组成的四元环链,在[0 1 0]、[0 4 15]和[0 -4 15]三个方向形成了三个交叉8元环孔道,有机胺阳离子起着平衡电荷和稳定骨架的结构。它的晶体数据为:[HO(CH2)2NH3]2•[Zn3(HPO3)4],M=640.21, 正交晶系, Fdd2空间群, a=2.8528, b=0.8426, c=1.6159nm, Z=8, V=3.884nm3, R1=0.0219, wR2=0.0544。  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