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   2937篇
  免费   543篇
  国内免费   323篇
化学   2144篇
晶体学   38篇
力学   184篇
综合类   20篇
数学   300篇
物理学   1117篇
  2024年   3篇
  2023年   88篇
  2022年   70篇
  2021年   115篇
  2020年   162篇
  2019年   138篇
  2018年   137篇
  2017年   85篇
  2016年   179篇
  2015年   140篇
  2014年   184篇
  2013年   197篇
  2012年   286篇
  2011年   318篇
  2010年   185篇
  2009年   218篇
  2008年   206篇
  2007年   159篇
  2006年   143篇
  2005年   115篇
  2004年   93篇
  2003年   74篇
  2002年   68篇
  2001年   57篇
  2000年   49篇
  1999年   53篇
  1998年   43篇
  1997年   34篇
  1996年   52篇
  1995年   28篇
  1994年   30篇
  1993年   15篇
  1992年   15篇
  1991年   16篇
  1990年   11篇
  1989年   10篇
  1988年   8篇
  1987年   3篇
  1986年   6篇
  1985年   2篇
  1984年   1篇
  1983年   2篇
  1982年   1篇
  1974年   1篇
  1957年   3篇
排序方式: 共有3803条查询结果,搜索用时 31 毫秒
31.
Shape modeling is fundamental to the analysis of dynamic environment and motion around asteroid. Chang'E- 2 successfully made a flyby of Asteroid 4179 Toutatis and obtained plenty of high-resolution images during the mis- sion. In this paper, the modeling method and preliminary model of Asteroid Toutatis are discussed. First, the optical images obtained by Chang'E-2 are analyzed. Terrain and silhouette features in images are described. Then, the modeling method based on previous radar model and preliminary information from optical images is proposed. A preliminary polyhedron model of Asteroid Toutatis is established. Finally, the spherical harmonic coefficients of Asteroid Toutatis based on the polyhedron model are obtained. Some parameters of model are analyzed and compared. Although the model proposed in this paper is only a preliminary model, this work offers a valuable reference for future high-resolution models.  相似文献   
32.
A novel method based on plastic processing and equipment for preparing ultra-fine metal fibers and particles is reported. With this new method, metal fibers and particles can both be produced on the same equipment and the surfaces of the fibers and particles can be protected from oxidation by the polymers or solvents during the preparation process. Metal-alloy powders with lower melt point were filled into polymer by an extruder, followed by a die-drawing process at a temperature lower than the melt temperature of the metal alloy. Metal fibers or particles were obtained after the polymer matrix was washed away. Metal alloy fibers can be obtained when a polymer that strongly interacts with metal alloy, such as a special polyvinyl alcohol with a low alcoholysis degree, is used as the polymer matrix. Metal-alloy particles can be obtained when a polymer with weak interaction with metal alloy, such as polyethylene (PE), is used as the polymer matrix. Based on the principle of this new method, it is possible to produce finer or even nano-sized metal fibers and particles with higher melting points.  相似文献   
33.
Tin (Sn) has been considered as an attractive anode material for sodium-ion batteries (SIBs) due to its high theoretical capacity (847 mAh g?1). Nevertheless, its low conductivity and large volume change during cycling essentially prevent the possibility of high capacity and long-term cycle for SIBs. In this work, Sn nanoparticles are well embedded into the highly ordered mesoporous carbon (CMK-3) matrix (Sn@CMK-3) using a facile sonochemical method combined with heat treatment. The resultant Sn@CMK-3 nanohybrid electrode delivers an initial charge capacity of 412 mAh g?1 at 100 mA g?1. A reversible capacity of 337 mAh g?1 is obtained after 200 cycles, indicating the good cycle stability of the nanohybrid structure. The electrode also shows a potential rate capability, which maintains a capacity of 228 mAh g?1 at 1000 mA g?1. When the current density returns to 50 mA g?1, the capacity goes back to 381 mAh g?1, with a capacity retention of 86.9%. The enhanced sodium storage performance of Sn@CMK-3 nanohybrid can be related to the synergistic effect between CMK-3 and Sn.
Graphical abstract Sn@CMK-3 nanohybrid with Sn nanoparticles uniformly distributed into the highly ordered mesoporous carbon matrix exhibited good cycling performance and rate capability.
  相似文献   
34.
In this paper, three new circulant operator matrices, scaled circulant operator matrices, diag-circulant operator matrices and retrocirculant operator matrices, are given respectively. Several norm equalities and inequalities for these operator matrices are proved. We show the special cases for norm equalities and inequalities, such as the usual operator norm and the Schatten p-norm. Pinching type inequality is also given for weakly unitarily invariant norms. These results are closely related to the nice structure of these special operator matrices. Furthermore, some special cases and specific examples are also considered.  相似文献   
35.
Let f(z) be a meromorphic function in the complex plane, whose zeros have multiplicity at least k + 1(k ≥ 2). If sin z is a small function with respect to f(z), then f~(k)(z)-P(z) sin z has infinitely many zeros in the complex plane, where P(z) is a nonzero polynomial of deg(P(z)) ≠ 1.  相似文献   
36.
Herein, we report a concise and divergent synthesis of the complex hasubanan alkaloids metaphanine and oxoepistephamiersine from commercially available and inexpensive cyclohexanedione monoethylene acetal. Our synthesis features a palladium-catalyzed cascade cyclization reaction to set the tricyclic carbon framework of the desired molecules, a regioselective Baeyer–Villiger oxidation followed by a MeNH2 triggered skeletal reorganization cascade to construct the benzannulated aza[4.4.3]propellane, and a strategically late-stage regio-/diastereoselective oxidative annulation of sp3 C−H bond to form the challenging THF ring system and hemiketal moiety in a single step. In addition, a highly enantioselective alkylation of cyclohexanedione monoethylene acetal paved the way for the asymmetric synthesis of target molecular.  相似文献   
37.
Single-atom catalysts exhibit superior CO2-to-CO catalytic activity, but poor kinetics of proton-coupled electron transfer (PCET) steps still limit the overall performance toward the industrial scale. Here, we constructed a Fe−P atom paired catalyst onto nitrogen doped graphitic layer (Fe1/PNG) to accelerate PCET step. Fe1/PNG delivers an industrial CO current of 1 A with FECO over 90 % at 2.5 V in a membrane-electrode assembly, overperforming the CO current of Fe1/NG by more than 300 %. We also decrypted the synergistic effects of the P atom in the Fe−P atom pair using operando techniques and density functional theory, revealing that the P atom provides additional adsorption sites for accelerating water dissociation, boosting the hydrogenation of CO2, and enhancing the activity of CO2 reduction. This atom-pair catalytic strategy can modulate multiple reactants and intermediates to break through the inherent limitations of single-atom catalysts.  相似文献   
38.
Heterogeneous single-metal-site catalysts usually suffer from poor stability, thereby limiting industrial applications. Dual Pd1−Ru1 single-atom-sites supported on porous ionic polymers (Pd1−Ru1/PIPs) were constructed using a wetness impregnation method. The two isolated metal species in the form of a binuclear complex were immobilized on the cationic framework of PIPs through ionic bonds. Compared to the single Pd- or Ru-site catalyst, the dual single-atom system exhibits higher activity with 98 % acetylene conversion and near 100 % selectivity to dialkoxycarbonylation products, as well as better cycling stability for ten cycles without obvious decay. Based on DFT calculations, it was found that the single-Ru site exhibited a strong CO adsorption energy of −1.6 eV, leading to an increase in the local CO concentration of the catalyst. Notably, the Pd1−Ru1/PIPs catalyst had a much lower energy barrier of 2.49 eV compared to 3.87 eV of Pd1/PIPs for the rate-determining step. The synergetic effect between neighboring single sites Pd1 and Ru1 not only enhanced the overall activity, but also stabilized PdII active sites. The discovery of synergetic effects between single sites can deepen our understanding of single-site catalysts at the molecular level.  相似文献   
39.
A Friedel–Crafts reaction of indolizines with 2-aryl-3H-indol-3-ones catalyzed by B(C6F5)3 is described. This protocol gives access to indolizine derivatives that are valuable building blocks in synthetic and pharmaceutical chemistry. The reaction proceeds under mild conditions, affording various C2-quaternary indolin-3-ones based on indolizine with high yields and regioselectivities. Moreover, the synthetic transformations of the target products were realized by N-methylation and trifluoromethane sulfonation.  相似文献   
40.
植物样品中各元素的含量,是评价土壤质量及健康的重要指标。为满足测定大批量生态地球化学植物样品中多金属元素分析要求,建立了交互模式-ICP-MS法测定植物样品中7种痕量金属元素的定量分析方法。讨论了ICP-MS的STD、KED(He)、交互模式3种方法测定植物样品中7种金属元素结果。实验结果表明:利用工作曲线法配制Hg标准溶液,更改82Se在线校正方程系数为1.83,在ICP-MS的交互模式下测定植物样品中82Se,63Cu,60Ni,66Zn,111Cd,75As、202Hg可以得到准确可靠的结果,克服了植物样品中Se和Hg元素测定的难题。基于所建方法各元素校准曲线系数>0.999;方法检出限为0.0004~0.08mg/kg;加标回收率在96.2%-107%之间;测定GBW10010a(大米)、GBW10012(玉米)、GBW10021(豆角)3种标准物质,结果均在参考值范围内,相对标准偏差RSD<10%。该方法前处理简单、灵敏度高、准确度高、分析速度快,适用于生态地球化学评价植物样品多金属元素同时测定。为地球化学调查工作中分析测试植物样品中金属多元素的快速测定提供了新思路。  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