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   471篇
  免费   24篇
  国内免费   5篇
化学   335篇
力学   30篇
数学   88篇
物理学   47篇
  2023年   2篇
  2022年   3篇
  2021年   15篇
  2020年   28篇
  2019年   27篇
  2018年   30篇
  2017年   30篇
  2016年   33篇
  2015年   21篇
  2014年   44篇
  2013年   57篇
  2012年   33篇
  2011年   39篇
  2010年   22篇
  2009年   25篇
  2008年   12篇
  2007年   17篇
  2006年   10篇
  2005年   17篇
  2004年   11篇
  2003年   5篇
  2002年   6篇
  2000年   1篇
  1999年   2篇
  1998年   1篇
  1997年   1篇
  1991年   1篇
  1984年   1篇
  1980年   1篇
  1977年   1篇
  1976年   2篇
  1970年   1篇
  1967年   1篇
排序方式: 共有500条查询结果,搜索用时 250 毫秒
441.
Most of research has been carried out for the development of electrocatalysts for hydrogen evolution reaction (HER), which are high activity and low cost. In this study, a practical, usable, highly active, cheap, and none noble metal catalyst was developed for HER. To this end, tungsten disulfide supported on silicon (WS2/Si) and on silicon nanoparticles (WS2/nano-Si) were prepared. To increase the catalytic activity of WS2/nano-Si, chemical etching was used to prepare WS2/nano-Si etched. The synthesized electrocatalysts were characterized using Fortier transform infrared spectroscopy, field emission scanning electron microscopy, X-ray photoelectron spectroscopy, and X-ray diffraction methods. To evaluate the electrochemical attributes of WS2/Si and WS2/n-Si before and after chemical etching, electrochemical impedance spectroscopy, linear sweep, and cyclic voltammetry were used. The electrochemical measurements indicated an intense activity of the WS2/nano-Si/etched, through a high density of the current and low overpotential for HER, with a small overpotential of 0.14 V, Tafel slopes as small as 45 mV dec?1, and large cathodic currents. These results show that through etching process of silicon in HF the quantities of the active sites have been changed and increased considerably.  相似文献   
442.
This article is devoted to combined convection heat transfer of nanofluids through a vertical channel filled with a homogeneous and isotropic porous medium. The flow is assumed to be fully developed and the “Brinkman extended Darcy” model is used for the flow in the porous media and “clear compatible” viscous dissipation model is considered. Also the model utilized for the nanofluid incorporates the effects of Brownian motion and thermophoresis. The governing momentum, energy, and nanopartices volume fraction equations are solved both analytically and numerically. The effects of the influential dimensionless parameters such as Brownian and thermophoresis parameters, mixed convection parameter (Gr/Re), Brinkman, Darcy and Lewis numbers on dimensionless velocity and temperature distributions and pressure drop are studied. Also, the results of the Nusselt number for the both left and right walls are presented and discussed.  相似文献   
443.
(Pyridine)(tetrahydroborato)zinc complex, (Py)Zn(BH4)2, can efficiently perform acetylation of a variety of aliphatic and aromatic amines with ethyl acetate under refluxing THF.  相似文献   
444.
An issue of considerable importance, how to allocate a common revenue in an equitable manner across a set of competing entities. This paper introduces a new approach to obtaining allocation common revenue on all decision making units (DMUs) in such a way that the relative efficiency is not changed. In this method for determining allocation common revenue dose not need to solving any linear programming. A numerical example is provided to illustrate the results of the analysis.  相似文献   
445.
A carbon-paste electrode spiked with 1-[4-(ferrocenyl ethynyl)phenyl]-1-ethanone was constructed by the incorporation of 1-[4-(ferrocenyl ethynyl)phenyl]-1-ethanone in a graphite powder silicon oil matrix. It shown by cyclic voltammetry and double potential-step chronoamperometry, which this ferrocene derivative modified a carbon-paste electrode, can catalyze the ascorbic acid oxidation in an aqueous buffered solution. It has been found that under the optimum conditions (pH 7.00), the oxidation of ascorbic acid at the surface of this carbon paste modified electrode occurs at a potential of about 260 mV less positive than that of an unmodified carbon-paste electrode. The catalytic oxidation peak current was linearly dependent on the ascorbic acid concentration, and a linear calibration curve was obtained in the range of 6 x 10(-5) M-7 x 10(-3) M of ascorbic acid with a correlation coefficient of 0.9997. The detection limit (2sigma) was determined to be 6.3 x 10(-5) M. This method was also used for the determination of ascorbic acid in some pharmaceutical samples, such as effervescent tablets, ampoules and multivitamin syrup, by using a standard addition method. The reliability of the method was established by a parallel determination against the official method.  相似文献   
446.
SbF3 as an efficient catalyst has been used for regioselective alcoholysis, acetolysis and hydrolysis of epoxides to the corresponding β-alkoxy, β-acetoxy alcohols, and 1,2-diols in high to excellent yields. This study also represents a convenient synthesis of vic-diacetates from ring-opening of epoxides with acetic anhydride.  相似文献   
447.
The formation mechanism of hollow micron-sized polystyrene (PS) particles having numerous dents on the surface, so-called cage-like particles, obtained from seeded dispersion polymerization (SDP) of 2-ethylhexyl methacrylate (EHMA) with low molecular weight (MW) PS particles stabilized by poly(vinyl alcohol) (PVA) in the presence of hexadecane droplets was investigated. It was found that association of poly(2-ethylhexyl methacrylate) (PEHMA)/hexadecane phases which occurs due to the instability of the obtained composite particles followed by a diffusion of PS ellipsoidal particles into each other is the main process responsible for the production of such unique morphology. Time course monitoring of the SDP showed that diffusion of hexadecane and/or PS and/or PEHMA phase into PS/PEHMA/hexadecane composite particles through PS shell which happens based on Ostwald ripening is the main phenomenon which results in the formation of the dents on the surface of final particles. Moreover, the experimental results revealed that in this reaction system, the polymerization develops in a faster manner rather than the SDP employing seed particles having higher MWs. Furthermore, it was observed that particles with different surface morphologies can be produced by using different hydrocarbons. The elimination of small particles which are produced in addition to the cage-like ones via decreasing the concentration of the stabilizer was another interesting finding of this research. The acquired results showed that unstable SDP is expected to be a new concept in polymerization-induced self-assembly (PISA) which employs instability of a dispersion for self-assembly of polymeric particles, and therefore, production of polymeric unique objects.  相似文献   
448.
An Al-doped ZnO@Fe3O4 nanocomposite was synthesized and used as a magnetic sorbent for solid-phase extraction of Cd(II) prior to its determination by flame atomic absorption spectrometry (FAAS). The size and morphology of the nano-sorbent were characterized via X-ray diffraction analysis, scanning electron microscopy and FTIR. Following its desorption with acetic acid, cadmium was quantified by FAAS. Factors affecting the extraction of the Cd(II) were optimized. Under optimized experimental conditions, the calibration graph is linear in the 0.6 to 60 ng mL?1 concentration range. The limit of detection is 0.17 ng mL?1 and the pre-concentration factor is 50. The inter- and intra-day relative standard deviations for six replicate determinations at a Cd(II) level of 40 ng mL?1 are 3.8% and 2.5%, respectively. The method was successfully applied to the trace determination of Cd(II) in spiked water samples. The accuracy of the method was confirmed by analyzing the certified reference material NIST SRM 1643e.
Graphical abstract Schematic of the synthesis of an Al-doped ZnO@Fe3O4 nanocomposite and its application as a magnetic sorbent for solid-phase extraction of Cd(II) prior to its determination by flame atomic absorption spectrometry (FAAS).
  相似文献   
449.
A new water-soluble Cu(II) complex containing ranitidine drug and 1,10-phenanthroline was synthesized and characterized by elemental analysis, molar conductivity, spectroscopic and computational methods. In vitro human serum albumin (HSA)-interaction studies of Cu(II) complex were performed by employing fluorescence spectroscopy in combination with UV–vis absorption and circular dichroism (CD) spectroscopies. The results of fluorescence titration showed that Cu(II) complex strongly quenched the intrinsic fluorescence of HSA through a static quenching mechanism with an intrinsic binding constant (6.05 × 104 M?1) at 286 K. The thermodynamic parameters ΔG, ΔH, and ΔS at different temperatures were calculated and suggested that the hydrophobic and hydrogen bonding interactions play major roles in Cu(II) complex-HSA association. The displacement experiments using warfarin and ibuprofen as site I and II probes proved that the Cu(II) complex could bind to site I (subdomain IIA) of HSA. Finally, CD spectra indicated that the interaction of the Cu(II) complex with HSA leads to an increase in the α-helical content. The main result of this study was the finding that the binding affinity of the Cu(II) complex to HSA is three orders of magnitude stronger than that of ranitidine drug.  相似文献   
450.
The present paper describes the synthesis of magnetically nanoparticles of zirconocene-modified magnetite, Fe3O4@APTMS@ZrCp2, as a new generation in heterogeneous and reusable type nanocatalysts. The prepared zirconocene nanocomposite was characterized using FT-IR, SEM, XRD, EDX, AGFM, ICP–OES, TGA and BET analyses. The core–shell nanocatalyst exhibited an excellent catalytic activity towards glycerol reduction of various nitro compounds to the corresponding amines. All reactions were carried out in H2O at room temperature (40–90 min) to afford amines in high to excellent yields. Reusability of the core–shell zirconocene was examined 5 times without significant loss of its catalytic activity.  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