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   109470篇
  免费   16457篇
  国内免费   11377篇
化学   74774篇
晶体学   1262篇
力学   6242篇
综合类   674篇
数学   12889篇
物理学   41463篇
  2025年   46篇
  2024年   1166篇
  2023年   2366篇
  2022年   4067篇
  2021年   4638篇
  2020年   5084篇
  2019年   4856篇
  2018年   3761篇
  2017年   3366篇
  2016年   5154篇
  2015年   4963篇
  2014年   6101篇
  2013年   7805篇
  2012年   9310篇
  2011年   9495篇
  2010年   6640篇
  2009年   6369篇
  2008年   6698篇
  2007年   5990篇
  2006年   5601篇
  2005年   4697篇
  2004年   3696篇
  2003年   2940篇
  2002年   2668篇
  2001年   2240篇
  2000年   1957篇
  1999年   2069篇
  1998年   1756篇
  1997年   1567篇
  1996年   1565篇
  1995年   1376篇
  1994年   1245篇
  1993年   1007篇
  1992年   903篇
  1991年   779篇
  1990年   659篇
  1989年   510篇
  1988年   388篇
  1987年   343篇
  1986年   343篇
  1985年   266篇
  1984年   195篇
  1983年   159篇
  1982年   133篇
  1981年   84篇
  1980年   59篇
  1979年   26篇
  1976年   22篇
  1975年   22篇
  1957年   26篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
51.
Sandwich ELISA methods have been widely used for biomarker and pathogen detection because of their high specificity and sensitivity. However, the main drawbacks of this assay are the cost, the time-consuming procedure for the isolation of antibodies and their poor stability. To overcome these restrictions, we herein fabricated artificial antibodies based on imprinting technology and developed a sandwich ELISA for pathogen detection. Both the capture and detection antibodies were obtained via an in situ method, with simplicity, rapidity and low cost. The peroxidase mimics, the CeO2 nanoparticles, as signal generators were integrated with the detection antibody. The fabricated artificial antibodies exhibited not only natural antibody-like binding affinities and selectivities, but also superior stability and reusability. The detection limit was about 500 CFU mL–1, which is much lower than that of traditional ELISA methods (104 to 105 CFU mL–1). Furthermore, the capture antibody can disinfect pathogens in situ.  相似文献   
52.
We have successfully produced open-mouthed, yolk–shell (OM-YS) Au@AgPd nanoparticles (NPs) via galvanic replacement reaction at room temperature; each NP has a large opening on its AgPd shells. Owing to the openings on the AgPd shells, the inner surfaces of the AgPd shells of as-prepared OM-YS Au@AgPd NPs become accessible to the surrounding media. These new structural characters make the present OM-YS Au@AgPd NPs excellent catalysts for electrochemical oxidation of ethanol in alkaline media. Their electrochemical active surface area is 87.8 m2 g–1 and the mass activity is 1.25 A mgPd–1. Moreover, the openings on the AgPd shells also make the surfaces of the Au cores in OM-YS Au@AgPd NPs accessible to the reaction media, which significantly facilitates the removal of CO and other carbonaceous intermediate species, thus leading to substantially enhanced durability and stability. This superior electrocatalytic performance cannot be implemented by using conventional YS Au@AgPd NPs or commercially available Pd/C catalysts.  相似文献   
53.
Structure–function correlations are a central theme in heterogeneous (photo)catalysis. In this study, the geometric and electronic structure of perovskite ferroelectric KNbO3 nanowires with respective orthorhombic and monoclinic polymorphs have been systematically addressed. By virtue of aberration-corrected scanning transmission electron microscopy, we directly visualize surface photocatalytic active sites, measure local atomic displacements at an accuracy of several picometers, and quantify ferroelectric polarization combined with first-principles calculations. The photoreactivity of the as-prepared KNbO3 nanowires is assessed toward aqueous rhodamine B degradation under UV light. A synergy between the ferroelectric polarization and electronic structure in photoreactivity enhancement is uncovered, which accounts for the prominent reactivity order: orthorhombic > monoclinic. Additionally, by identifying new photocatalytic products, rhodamine B degradation pathways involving N-deethylation and conjugated structure cleavage are proposed. Our findings not only provide new insights into the structure–photoreactivity relationships in perovskite ferroelectric photocatalysts, but also have broad implications in perovskite-based water splitting and photovoltaics, among others.  相似文献   
54.
The title compound, (C20H20P)[Cd(C2N3)3], consists of ethyltriphenylphosphonium (EtPh3P+) cations filling voids in a three‐dimensional anionic cadmium dicyanamide network. In the structure, each CdII atom is connected to six neighbouring CdII atoms through six separate dicyanamide ligands, forming cube‐shaped cages. The three‐dimensional anionic network encloses a solvent‐accessible void space of 1851 Å3, amounting to 69.3% of the unit‐cell volume. Each cage accommodates only one EtPh3P+ cation.  相似文献   
55.
Nanomaterials with both superhydrophobic surface properties as well as photocatalytic activities could have important industrial applications. Herein, we synthesized CeVO4 nanocrystals with hexagonal nanoplate structures from the reaction of decavanadate (K6V10O28⋅9 H2O) and CeCl3⋅H2O precursors via a hydrothermal method. This synthetic route has four advantages: 1) the reaction condition is relatively mild, 2) it doesn′t need surfactants or templates, 3) it requires no expensive equipment, and 4) products are of higher purity. During synthesis, solution pH, and reaction temperature were found to play important roles in determining the growth process and final morphologies of the CeVO4 products. These products were characterized spectrophotometrically and via scanning and transmission electron microscopy. Furthermore, the wettability of the as-synthesized film CeVO4 nanoplates was studied by measuring water contact angle (CA). The largest CA measured was at 169.5 ° for a glass substrate treated with 0.06 g mL−1 CeVO4 followed by 2 % 1 H, 1 H, 2 H, 2 H-perfluorodecyltriethoxysilane. Finally, the CeVO4 nanoplates exhibited excellent photocatalytic activity in degradation of rhodamine B (RhB) under UV irradiation and was stable even after repeated cycles of use.  相似文献   
56.
The reaction of N2 with trinuclear niobium and tungsten sulfide clusters Nb3Sn and W3Sn (n=0–3) was systematically studied by density functional theory calculations with TPSS functional and Def2-TZVP basis sets. Dissociations of N−N bonds on these clusters are all thermodynamically allowed but with different reactivity in kinetics. The reactivity of Nb3Sn is generally higher than that of W3Sn. In the favorite reaction pathways, the adsorbed N2 changes the adsorption sites from one metal atom to the bridge site of two metal atoms, then on the hollow site of three metal atoms, and at that place, the N−N bond dissociates. As the number of ligand S atoms increases, the reactivity of Nb3Sn decreases because of the hindering effect of S atoms, while W3S and W3S2 have the highest reactivity among four W3Sn clusters. The Mayer bond order, bond length, vibrational frequency, and electronic charges of the adsorbed N2 are analyzed along the reaction pathways to show the activation process of the N−N bond in reactions. The charge transfer from the clusters to the N2 antibonding orbitals plays an essential role in N−N bond activation, which is more significant in Nb3Sn than in W3Sn, leading to the higher reactivity of Nb3Sn. The reaction mechanisms found in this work may provide important theoretical guidance for the further rational design of related catalytic systems for nitrogen reduction reactions (NRR).  相似文献   
57.
Qin  Kaiwei  Guo  Lei  Ming  Shujun  Zhang  Shoute  Guo  Yanbin  Pang  Lei  Li  Tao 《Catalysis Surveys from Asia》2022,26(2):115-128
Catalysis Surveys from Asia - The catalytic performances and mechanism differences of model catalysts Cu–SSZ-13 and Fe–SSZ-13 with similar metal content and Si/Al ratio were compared....  相似文献   
58.
Li  Baixue  Li  Zhen  You  Kai  Qin  Anjun  Tang  Ben Zhong 《中国科学:化学(英文版)》2022,65(4):771-777
Science China Chemistry - Secrecy has received tremendous attention in modern information society. Innovative polymer-based fluorescent materials with multiple mode emission are quite desirable to...  相似文献   
59.
Cyclic organic amines are emerging as excellent building blocks to assemble organic–inorganic hybrid phase transition materials due to their flexible cyclic structure. Here, we have assembled a 1D organic-inorganic hybrid dielectric material C5H6NOPbBr3 ( 1 ) by alloying the cyclic organic amine 3-hydroxypyridine. 1 displays a remarkable switchable dielectric response induced by an order-disorder transformation of the organic moiety, this transformation behaviour is confirmed by DSC and Hirshfeld surface measurements. More interestingly, 1 has a narrowband emission (FWHM=4.64 nm) at 590 nm; FWHM is a major quality figure for narrowband photodetectors. In addition, 1 exhibits semiconducting properties with an indirect bandgap of 2.78 eV by the analysis of the UV-Vis absorption results.  相似文献   
60.
An electro-oxidative cyclization pathway in which hydrazones are selected as starting materials to generate amphiphiles by reacting with benzylamines and benzamides was reported. This strategy successfully prepared a series of 1,2,4-triazoles in satisfactory yields. Moreover, the use of cheap stainless steel as the anode, the feasibility to conduct the transformation as a one-pot reaction and the proof that scaling-up these reactions is possible make this transformation attractive for potential application in industry.  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