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   18478篇
  免费   1728篇
  国内免费   2356篇
化学   12162篇
晶体学   120篇
力学   985篇
综合类   115篇
数学   1004篇
物理学   2807篇
综合类   5369篇
  2024年   84篇
  2023年   229篇
  2022年   578篇
  2021年   633篇
  2020年   866篇
  2019年   689篇
  2018年   493篇
  2017年   565篇
  2016年   633篇
  2015年   662篇
  2014年   842篇
  2013年   1237篇
  2012年   1072篇
  2011年   940篇
  2010年   735篇
  2009年   893篇
  2008年   914篇
  2007年   1058篇
  2006年   980篇
  2005年   936篇
  2004年   916篇
  2003年   783篇
  2002年   800篇
  2001年   560篇
  2000年   583篇
  1999年   476篇
  1998年   406篇
  1997年   425篇
  1996年   356篇
  1995年   392篇
  1994年   332篇
  1993年   267篇
  1992年   259篇
  1991年   184篇
  1990年   160篇
  1989年   148篇
  1988年   125篇
  1987年   97篇
  1986年   46篇
  1985年   39篇
  1984年   26篇
  1983年   18篇
  1982年   24篇
  1981年   18篇
  1980年   21篇
  1979年   15篇
  1978年   10篇
  1977年   8篇
  1976年   10篇
  1973年   8篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
231.
H 0 and S 0 values of the complex formation in water of benzo-18-crown-6 (B18C6) with K+, Tl+, and Pb2+ were determined and compared with those of 18-crown-6. The H0 values of B18C6 are negative. The stability in water of the B18C6-metal ion complex at 25°C is governed largely by the magnitude of the H 0 value. The B18C6-metal ion complex is less stable in water than the corresponding 18C6-metal ion complex. This is due largely to a less favorable enthalpic contribution of the B18C6-metal ion complex compared with the corresponding 18C6-metal ion complex. The two aromatic ether oxygen atoms of B18C6 are responsible for the larger H 0 value of the B18C6-metal ion complex compared with the corresponding 18C6-metal ion complex.  相似文献   
232.
The water gas shift reaction (CO + H2O = CO2+ H2) is catalyzed by aqueous metal carbonyl systems derived from simple mononuclear carbonyls such as Fe(CO)5 and M(CO)6 (M = Cr, Mo, and W) and bases in the 140–200 °C temperature range. The water gas shift reaction in a basic methanol-water solution containing Fe(CO)5 is first order in [Fe(CO)5], zero order in [CO], and essentially independent of base concentration and appears to involve an associative mechanism with a metallocarboxylate intermediate [(CO)4Fe-CO2H]. The water gas shift reactions using M(CO)6 as catalyst precursors are first order in [M(CO)6], inverse first order in [CO], and first order in [HCO2 ] and appear to involve a dissociative mechanism with formatometallate intermediates [(CO)5M-OCHO].The Reppe hydroformylation of ethylene to produce propionaldehyde and 1-propanol in basic solutions containing Fe(CO)5 occurs at 110–140 °C. This reaction is second order in [Fe(CO)5], first order in [C2H4] up to a saturation pressure >1.5 MPa, and inhibited by [CO]. These experimental results suggest a mechanism where the rate-determining step involves a binuclear iron carbonyl intermediate. The substitution of Et3N for NaOH as the base facilitates the reduction of propionaldehyde to 1-propanol but results in a slower rate for the overall reaction.The homogeneous photocatalytic decomposition of the formate ion to H2 and CO2 in the presence of Cr(CO)6 appears to be closely related to the water gas shift reaction. The rate of H2 production from the formate ion exhibits saturation kinetics in the formate ion and is inhibited by added pyridine. The infrared spectra of the catalyst solutions indicate an LCr(CO)5 intermediate. Photolysis of the Cr(CO)6/formate system in aqueous methanol in the presence of an aldehyde RCHO (R =n-heptyl,p-tolyl, andp-anisyl) results in catalytic hydrogenation of the aldehyde to the corresponding alcohol RCH2OH by the formate ion. Detailed kinetic studies onp-tolualdehyde hydrogenation by this method indicates saturation kinetics in formate ion, autoinhibition by thep-tolualdehyde, and a threshold effect for Cr(CO)6 at concentrations >0.004 mol L–1. The presence of an aldehyde can interrupt the water gas shift catalytic cycle by interception of an HCr(CO)5 intermediate by the aldehyde.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1533–1539, September, 1994.  相似文献   
233.
应用溶剂化金属原子浸渍法和普通浸渍法制备了三种不同摩尔比的γ-Al2O3负载Ni-Ag双金属催化剂。XRD和磁测定结果表明SMAI催化剂中Ni和Ag的粒度均小于金属相同的CI催化剂。SMAI催化剂中Ni和Ag未形成合金,而CI催化剂中Ni和Ag形成了合金。  相似文献   
234.
烯丙位氧化的几种方法   总被引:4,自引:0,他引:4  
李春  司伊康 《有机化学》2003,23(6):518-525
综述了近年来烯丙位氧化的研究进展,详细讨论了过渡金属及其络合物、硒化 合物在烯丙位氧化中的应用,并简述了丁基锂方法、固相催化方法、生物氧化方法 和次氯酸钠氧化方法在烯丙位氧化中的应用.  相似文献   
235.
催化燃烧是目前最有效的处理挥发性有机物(VOCs)技术之一. 本文从催化剂活性组分、催化剂载体、有效组分颗粒大小、水蒸汽的影响及催化燃烧反应中的积碳等几个方面, 对近年来催化燃烧处理VOCs的研究进行了总结. 分析表明: 贵金属催化剂的研究主要着重于选择有效的载体和双组分贵金属催化剂; 非贵金属催化剂的研究主要集中在高活性的过渡金属复合氧化物、钙钛矿和尖晶石型等催化剂的研制, 还有这些活性组分粒径大小及载体对催化燃烧VOCs反应活性的影响;此外, 在实际应用中,水蒸汽和催化剂积碳失活等问题对催化燃烧VOCs的反应也有很大影响. 本文的评述将为选择合适的催化燃烧技术处理VOCs污染物提供一定参考.  相似文献   
236.
In a mass spectrometric study, it was found that the saturated vapor over gadolinium tris-hexafluoroacetylacetonate Gd(C5O2HF6)3 contains molecular forms with a mass exceeding the mass of the dimer. The vapor overheated to 250–300°C contains only the monomer form. Simultaneous electron diffraction and mass spectrometric experiment aimed at investigating the structure of the Gd(hfa)3 monomer molecule was carried out at 284(5)°C. The Gd(hfa)3 molecule was found to have the symmetry of the equilibrium D 3 configuration. The basic structural parameters are r h1(Gd-O) = 2.291(10) Å, r h1(O-C) = 1.257(10) Å, r h1(C-Cr) = 1.404(6) Å, r h1(CF-F)av = 1.341(3) Å, ∠OGdO = 72.8(0.4)°. The GdO6 coordination polyhedron has the structure of a distorted antiprism. The rotation angle of the O-O-O trigonal faces relative to their position in a regular prism is 18.7(0.9)°. Quantum chemical calculations (HF/SBK, 6-31G*) generally reproduce the experimental structure, but the Gd-O internuclear distance is exaggerated by 0.04 Å.  相似文献   
237.
Since its inception five decades ago, imprinted sol-gel materials went practically unnoticed, until in the 1970s the conceptual introduction of molecular imprinting in synthetic polymers triggered a new interest in this field. The recent growth in interest in organic–inorganic hybrid materials prepared by sol-gel chemistry and the development of a variety of new strategies for imprinting polymeric matrices have led to a growing activity in what became known as molecularly imprinted sol-gel materials. This paper intends to give an overview of recent progress in molecular imprinting in sol-gel matrices, the potential analytical applications of these tailor-made materials and their limitations, with the aim of drawing attention to useful information and to enhancing interest in this practically unexplored but promising field.  相似文献   
238.
Models of alkali metal hydroxide-water-dimethylsulfoxide superbasic media have been constructed using Hartree Fock and DFT (B3LYP) quantum chemical methods; the structure and energies of anion complexes are considered. The hydroxide anion in the models is stabilized as complexes of OH?·H2O and OH?· 2H2O types.  相似文献   
239.
《Electroanalysis》2005,17(20):1861-1864
Electrochemical study of barley grain lipid‐transfer protein (LTP) revealed that it may belong to the metal‐binding protein class. Using differential pulse polarography the presence of Cu(II) and Zn(II) ions in the native LTP structure was proved, as well as its affinity for binding Ni(II) ion. Application of a more sensitive electroanalytical technique, such as anodic stripping voltammetry with analyte preconcentration, revealed the presence of Pb(II) and Cd(II) ions and also enabled the following Hg(II) ion binding. Possible biological role of LTP in plant stress response and its contribution to barley phytoextraction potential are discussed.  相似文献   
240.
Adsorption of Pb2+ ions on the combustion derived nanosized γ-Fe2O3 and its thiourea complex composite is reported. The adsorbents upon adsorption of Pb2+ ions are characterised by X-ray diffraction, scanning electron microscopy, energy dispersive X-ray microanalysis and infrared spectroscopy techniques. The eluent is characterised by atomic absorption spectroscopy for the estimation of Pb2+ ions. The reduction in the amount of lead after adsorption was estimated to be around 50% in case of complex composite adsorbent and around 15% in case of the γ-Fe2O3 adsorbents. Orthorhombic PbSO4 precipitated out from the eluent and is reported with a model reaction. Adsorption of lead onto the complex composite is explained through the formation of a surface tertiary complex. The advantage of employing a thiourea-γ-Fe2O3 complex composite as solid adsorbent for the adsorption of heavy metal pollutants is envisaged in the present investigation.  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