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   291篇
  免费   27篇
  国内免费   31篇
化学   209篇
晶体学   1篇
力学   15篇
数学   50篇
物理学   74篇
  2023年   1篇
  2022年   7篇
  2021年   8篇
  2020年   10篇
  2019年   8篇
  2018年   10篇
  2017年   9篇
  2016年   11篇
  2015年   7篇
  2014年   11篇
  2013年   22篇
  2012年   19篇
  2011年   30篇
  2010年   11篇
  2009年   17篇
  2008年   22篇
  2007年   22篇
  2006年   14篇
  2005年   12篇
  2004年   20篇
  2003年   16篇
  2002年   17篇
  2001年   12篇
  2000年   8篇
  1999年   8篇
  1998年   2篇
  1997年   2篇
  1996年   3篇
  1994年   1篇
  1993年   2篇
  1991年   1篇
  1990年   1篇
  1989年   1篇
  1987年   1篇
  1985年   1篇
  1979年   2篇
排序方式: 共有349条查询结果,搜索用时 421 毫秒
21.
The semihydrogenation of alkynes into alkenes rather than alkanes is of great importance in the chemical industry. Unfortunately, state-of-the-art heterogeneous catalysts hardly achieve high turnover frequencies (TOFs) simultaneously with almost full conversion, excellent selectivity, and good stability. Here, we used metal–organic frameworks (MOFs) containing Zr metal nodes (“UiO”) with tunable wettability and electron-withdrawing ability as activity accelerators for the semihydrogenation of alkynes catalyzed by sandwiched palladium nanoparticles (Pd NPs). Impressively, the porous hydrophobic UiO support not only leads to an enrichment of phenylacetylene around the Pd NPs but also renders the Pd surfaces more electron-deficient, which leads to a remarkable catalysis performance, including an exceptionally high TOF of 13835 h−1, 100 % phenylacetylene conversion 93.1 % selectivity towards styrene, and no activity decay after successive catalytic cycles. The strategy of using molecularly tailored supports is universal for boosting the selective semihydrogenation of various terminal and internal alkynes.  相似文献   
22.
23.
Making a revision of mistakes in Ref. [19], we present a detailed study of the competition and interplay between the d-density wave (DDW) and d-wave superconductivity (DSC) within the fluctuation-exchange (FLEX) approximation for the two-dimensional (2D) Hubbard model. In order to stabilize the DDW state with respect to phase separation at lower dopings a small nearest-neighbor Coulomb repulsion is included within the Hartree-Fock approximation. We solve the coupled gap equations for the DDW, DSC, and π-pairing as the possible order parameters, which are caused by exchange of spin fluctuations, together with calculating the spin fluctuation pairing interaction self-consistently within the FLEX approximation. We show that even when nesting of the Fermi surface is perfect, as in a square lattice with only nearest-neighbor hopping, there is coexistence of DSC and DDW in a large region of dopings close to the quantum critical point (QCP) at which the DDW state vanishes. In particular, we find that in the presence of DDW order the superconducting transition temperature Tc can be much higher compared to pure superconductivity, since the pairing interaction is strongly enhanced due to the feedback effect on spin fluctuations of the DDW gap. π-pairing appears generically in the coexistence region, but its feedback on the other order parameters is very small. In the present work, we have developed a weak-coupling theory of the competition between DDW and DSC in 2D Hubbard model, using the static spin fluctuation obtained within FLEX approximation and ignoring the self-energy effect of spin fluctuations. For our model calculations in the weak-coupling limit we have taken U/t=3.4, since the antiferromagnetic instability occurs for higher values of U/t.  相似文献   
24.
Developing of a simple method for the fabrication of superparamagnetic iron oxide nanoparticles (Nps) is still a challenge for materials scientists. This work reveals a way to fabricate especially stable ferrofluids from spherical Nps of magnetite using the co-precipitation method, for which a new (diglycolic acid) stabilizer was applied. The Nps of the average size of ~7.4–16.5 nm were characterized by means of high resolution transmission electron microscopy (HRTEM), atomic force microscopy (AFM), selective area electron diffraction (SAED), Raman, FTIR and Mössbauer spectroscopy. The stabilization effect of the diglycolic acid for the growth of superparamagnetic Nps growth was discussed on the basis of experimental results.  相似文献   
25.
A glassy carbon electrode having two polymer layers has been applied to selectively detect epinephrine. The inner layer formed by electropolymerization of macrocyclic nickel complex functioned as an electrocatalyst for epinephrine oxidation and the outer layer composed of hydrolyzed polyurethane γ‐benzyl L ‐glutamate as a screening layer. Differential pulse voltammetry showed almost 100% recovery of epinephrine even in 100‐fold excess of interferents. When applied to a dual glassy carbon electrode as an amperometric detector in flow injection analysis, a linear response over 0.1 μM and 10 μM was obtained. Recovery tested for 5‐fold diluted human urine samples was 97.5%.  相似文献   
26.
The photoluminescence (PL) of GaN quantum dots in an AlN matrix is studied. It is found that the maximum of the PL line does not shift when the laser excitation power varies. The transient PL spectra indicate that the quenching kinetics is nonexponential and the quenching law depends on the spectral range. The experimental data are explained in the framework of a model taking into account the strong built-in electric field in wurtzite structures and the transport of charge carriers between them.  相似文献   
27.
The gamma function and its various modifications such as the (upper) incomplete, regularized and inverted-regularized incomplete gamma functions are of importance in both theory and applications. In this note we observe an ‘if and only if ’ relationship between a certain axiom of insurance risk management and a monotonicity property of the composition of regularized and inverted-regularized incomplete gamma functions, assuming that the risks follow gamma distributions. We derive the monotonicity property by utilizing the above noted relationship and a probabilistic technique. The aforementioned insurance axiom, called consistent no-undercut, is explained in detail and related to several techniques of analysis.  相似文献   
28.
The total amplitude reflection coefficient of EM wave in a nonuniform plasma slab coated on perfect conductor plane is newly derived by using the scattering matrix method (SMM), and the attenuation is calculated. Three types of plasma electron density profile, that is the hyperbolic, sinusoidal, and linear profiles, are used. The external magnetic field and plasma parameters such as the maximum electron density and collision frequencies are discussed to calculate the attenuation of EM wave. The calculation results show that the plasma electron density profile and maximum electron density exert a large effect to the attenuation of EM wave and the attenuation under the uniform external magnetic field is taken place by the electron cyclotron resonance absorption, the up hybrid resonance absorption and geometric resonances absorption.  相似文献   
29.
A facile method for solid‐phase organic synthesis of 1‐substituted‐4‐vinyl‐1,2,3‐triazoles from polystyrene‐supported but‐3‐ynyl selenide has been developed. This sequential [3+2] cycloaddition and oxidation–elimination reactions could be carried out under mild reaction conditions with straightforward operation and good yield and purity of the products, and broad scope of substrates, and could be applied in this reaction system in generation of a small library of title compounds.  相似文献   
30.
<正>A novel polyamide containing xanthene structure and trifluoromethylphenoxy pendent was prepared from 9,9-bis[4-(4- aminophenoxy)phenyl]xanthene,a novel diamine with 2-(4-trifluoromethylphenoxy)terephthaloyl chloride,by the low temperature polycondensation.This new polyamide with the inherent viscosity of 0.95 dL/g was amorphous and readily soluble in polar solvents such as DMAc,m-cresol,etc.This polyamide showed the glass transition temperature(T_g) of 236℃,decomposition temperature (Td) at 5%weight loss of 455℃and char yield of 56%at 800℃in N_2.Transparent,flexible,and tough film of the polymer cast from DMAc solution exhibited tensile strength of 93 MPa,elongation at break of 14%,initial moduli of 2.2 GPa.The electric properties such as the dielectric constant of 3.03(1 MHz) and surface resistance(2.78×10~(14)Ω),and the moisture uptake of 1.36% were also described.  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