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:从到   被引次数:从到   他引次数:从到 提示：输入*表示无穷大
全文获取类型
  收费全文   14648篇
  免费   1603篇
  国内免费   2224篇
专业分类
化学   14064篇
晶体学   257篇
力学   417篇
综合类   86篇
数学   218篇
物理学   3433篇
出版年
  2025年   7篇
  2024年   214篇
  2023年   273篇
  2022年   686篇
  2021年   781篇
  2020年   1093篇
  2019年   985篇
  2018年   612篇
  2017年   670篇
  2016年   773篇
  2015年   753篇
  2014年   859篇
  2013年   1435篇
  2012年   1010篇
  2011年   1025篇
  2010年   761篇
  2009年   776篇
  2008年   753篇
  2007年   724篇
  2006年   630篇
  2005年   593篇
  2004年   567篇
  2003年   463篇
  2002年   357篇
  2001年   297篇
  2000年   224篇
  1999年   201篇
  1998年   187篇
  1997年   137篇
  1996年   109篇
  1995年   117篇
  1994年   85篇
  1993年   88篇
  1992年   38篇
  1991年   37篇
  1990年   28篇
  1989年   15篇
  1988年   18篇
  1987年   14篇
  1986年   11篇
  1985年   10篇
  1984年   11篇
  1983年   10篇
  1982年   7篇
  1981年   7篇
  1980年   5篇
  1979年   7篇
  1976年   2篇
  1975年   2篇
  1972年   4篇
排序方式： 共有10000条查询结果，搜索用时 0 毫秒
81.
    
Cumulene compounds are notoriously difficult to prepare and study because their reactivity increases dramatically with the increasing number of consecutive double bonds. In this respect, the emerging field of on-surface synthesis provides exceptional opportunities because it relies on reactions on clean metal substrates under well-controlled ultrahigh-vacuum conditions. Here we report the on-surface synthesis of a polymer linked by cumulene-like bonds on a Au(111) surface via sequential thermally activated dehalogenative C−C coupling of a tribenzoazulene precursor equipped with two dibromomethylene groups. The structure and electronic properties of the resulting polymer with cumulene-like pentagon–pentagon and heptagon–heptagon connections have been investigated by means of scanning probe microscopy and spectroscopy methods and X-ray photoelectron spectroscopy, complemented by density functional theory calculations. Our results provide perspectives for the on-surface synthesis of cumulene-containing compounds, as well as protocols relevant to the stepwise fabrication of carbon–carbon bonds on surfaces.  相似文献   
82.
    
Continued efforts are made for the utilization of CO2 as a C1 feedstock for regeneration of valuable chemicals and fuels. Mechanistic study of molecular (electro-/photo-)catalysts disclosed that initial step for CO2 activation involves either nucleophilic insertion or direct reduction of CO2. In this study, nucleophilic activation of CO2 by complex [(NO)2Fe(μ-MePyr)2Fe(NO)2]2− ( 2 , MePyr=3-methylpyrazolate) results in the formation of CO2-captured complex [(NO)2Fe(MePyrCO2)]− ( 2-CO2 , MePyrCO2=3-methyl-pyrazole-1-carboxylate). Single-crystal structure, spectroscopic, reactivity, and computational study unravels 2-CO2 as a unique intermediate for reductive transformation of CO2 promoted by Ca2+. Moreover, sequential reaction of 2 with CO2, Ca(OTf)2, and KC8 established a synthetic cycle, 2 → 2-CO2 → [(NO)2Fe(μ-MePyr)2Fe(NO)2] ( 1 ) → 2 , for selective conversion of CO2 into oxalate. Presumably, characterization of the unprecedented intermediate 2-CO2 may open an avenue for systematic evaluation of the effects of alternative Lewis acids on reduction of CO2.  相似文献   
83.
    
Glassy polyimide membranes are attractive for industrial applications in sour natural gas purification. Unfortunately, the lack of fundamental understanding of relationships between polyimide chemical structures and their gas transport properties in the presence of H2S constrains the design and engineering of advanced membranes for such challenging applications. Herein, 6FDA-based polyimide membranes with engineered structures were synthesized to tune their CO2/CH4 and H2S/CH4 separation performances and plasticization properties. Under ternary mixed sour gas feeds, controlling polymer chain packing and plasticization tendency of such polyimide membranes via tuning the chemical structures were found to offer better combined H2S and CO2 removal efficiency compared to conventional polymers. Fundamental insights into structure–property relationships of 6FDA-based polyimide membranes observed in this study offer guidance for next generation membranes for sour natural gas separation.  相似文献   
84.
    
Simultaneously improving energy efficiency (EE) and material stability in electrochemical CO2 conversion remains an unsolved challenge. Among a series of ternary Sn-Ti-O electrocatalysts, 3D ordered mesoporous (3DOM) Sn0.3Ti0.7O2 achieves a trade-off between active-site exposure and structural stability, demonstrating up to 71.5 % half-cell EE over 200 hours, and a 94.5 % Faradaic efficiency for CO at an overpotential as low as 430 mV. DFT and X-ray absorption fine structure analyses reveal an electron density reconfiguration in the Sn-Ti-O system. A downshift of the orbital band center of Sn and a charge depletion of Ti collectively facilitate the dissociative adsorption of the desired intermediate COOH* for CO formation. It is also beneficial in maintaining a local alkaline environment to suppress H2 and formate formation, and in stabilizing oxygen atoms to prolong durability. These findings provide a new strategy in materials design for efficient CO2 conversion and beyond.  相似文献   
85.
    
The development of ultrastable carbon materials for potassium storage poses key limitations caused by the huge volume variation and sluggish kinetics. Nitrogen-enriched porous carbons have recently emerged as promising candidates for this application; however, rational control over nitrogen doping is needed to further suppress the long-term capacity fading. Here we propose a strategy based on pyrolysis–etching of a pyridine-coordinated polymer for deliberate manipulation of edge-nitrogen doping and specific spatial distribution in amorphous high-surface-area carbons; the obtained material shows an edge-nitrogen content of up to 9.34 at %, richer N distribution inside the material, and high surface area of 616 m2 g−1 under a cost-effective low-temperature carbonization. The optimized carbon delivers unprecedented K-storage stability over 6000 cycles with negligible capacity decay (252 mA h g−1 after 4 months at 1 A g−1), rarely reported for potassium storage.  相似文献   
86.
In situ exsolution of metal nanoparticles in perovskite under reducing atmosphere is employed to generate a highly active metal–oxide interface for CO2 electrolysis in a solid oxide electrolysis cell. Atomic-scale insight is provided into the exsolution of CoFe alloy nanoparticles in La0.4Sr0.6Co0.2Fe0.7Mo0.1O3−δ (LSCFM) by in situ scanning transmission electron microscopy (STEM) with energy-dispersive X-ray spectroscopy and DFT calculations. The doped Mo atoms occupy B sites of LSCFM, which increases the segregation energy of Co and Fe ions at B sites and improves the structural stability of LSCFM under a reducing atmosphere. In situ STEM measurements visualized sequential exsolution of Co and Fe ions, formation of CoFe alloy nanoparticles, and reversible exsolution and dissolution of CoFe alloy nanoparticles in LSCFM. The metal–oxide interface improves CO2 adsorption and activation, showing a higher CO2 electrolysis performance than the LSCFM counterparts.  相似文献   
87.
    
Mesoporous core–shell nanostructures with controllable ultra-large open channels in their nanoshells are of great interest. However, soft template-directed cooperative assembly to mesoporous nanoshells with highly accessible pores larger than 30 nm, or even above 50 nm into macroporous range, remains a significant challenge. Herein we report a general approach for precisely tailored coating of hierarchically macro-/mesoporous polymer and carbon shells, possessing highly accessible radial channels with extremely wide pore size distribution from ca. 10 nm to ca. 200 nm, on diverse functional materials. This strategy creates opportunities to tailor the interfacial assembly of irregular mesostructured nanounits on core materials and generate various core–shell nanomaterials with controllable pore architectures. The obtained Fe,N-doped macro-/mesoporous carbon nanoshells show enhanced electrochemical performance for the oxygen reduction reaction in alkaline condition.  相似文献   
88.
    
Previous density-functional theory (DFT) calculations show that sub-nanometric Cu clusters (i.e., 13 atoms) favorably generate CH4 from the CO2 reduction reaction (CO2RR), but experimental evidence is lacking. Herein, a facile impregnation-calcination route towards Cu clusters, having a diameter of about 1.0 nm with about 10 atoms, was developed by double confinement of carbon defects and micropores. These Cu clusters enable high selectivity for the CO2RR with a maximum Faraday efficiency of 81.7 % for CH4. Calculations and experimental results show that the Cu clusters enhance the adsorption of *H and *CO intermediates, thus promoting generation of CH4 rather than H2 and CO. The strong interactions between the Cu clusters and defective carbon optimize the electronic structure of the Cu clusters for selectivity and stability towards generation of CH4. Provided here is the first experimental evidence that sub-nanometric Cu clusters facilitate the production of CH4 from the CO2RR.  相似文献   
89.
Hydride abstraction from the heterocyclic carbene borane adducts (NHC)BH2C6F5 (NHC: IMes or IMe4) gave the B−H containing [(NHC)B(H)C6F5]+ borenium cations. They added carbon monoxide to give the respective [(NHC)B(H)(C6F5)CO]+ boron carbonyl cations. Carbon nucleophiles add to the boron carbonyl to give [B](H) acyls. Hydride reduced the [B]CO cation to hydroxymethylborane derivatives.  相似文献   
90.
    
The development of new principles and techniques with high neuronal compatibility for quantitatively monitoring the dynamics of neurochemicals is essential for deciphering brain chemistry and function but remains a great challenge. We herein report a neuron-compatible method for in vivo neurochemical sensing by powering a single carbon fiber through spontaneous bipolar electrochemistry as a new sensing platform. By using ascorbic acid as a model target to prove the concept, we found that the single-carbon-fiber-powered microsensor exhibited a good response, high stability and, more importantly, excellent neuronal compatibility. The microsensor was also highly compatible with electrophysiological recording, thus enabling the synchronous recording of both chemical and electrical signals. The sensing principle could be developed for in vivo monitoring of various neurochemicals in the future by rationally designing and tuning the electrochemical reactions at the two poles of the carbon fiber.  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