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   5033篇
  免费   182篇
  国内免费   19篇
化学   3605篇
晶体学   54篇
力学   118篇
数学   251篇
物理学   1206篇
  2023年   24篇
  2021年   40篇
  2020年   57篇
  2019年   67篇
  2018年   46篇
  2017年   40篇
  2016年   112篇
  2015年   96篇
  2014年   122篇
  2013年   245篇
  2012年   288篇
  2011年   366篇
  2010年   165篇
  2009年   151篇
  2008年   297篇
  2007年   254篇
  2006年   286篇
  2005年   260篇
  2004年   263篇
  2003年   229篇
  2002年   175篇
  2001年   128篇
  2000年   100篇
  1999年   61篇
  1998年   41篇
  1997年   48篇
  1996年   56篇
  1995年   45篇
  1994年   59篇
  1993年   51篇
  1992年   69篇
  1991年   43篇
  1990年   45篇
  1989年   51篇
  1988年   46篇
  1987年   45篇
  1986年   40篇
  1985年   83篇
  1984年   80篇
  1983年   33篇
  1982年   42篇
  1981年   39篇
  1980年   41篇
  1979年   71篇
  1978年   51篇
  1977年   55篇
  1976年   49篇
  1975年   33篇
  1974年   26篇
  1973年   19篇
排序方式: 共有5234条查询结果,搜索用时 15 毫秒
1.
This study examined the effects of OH concentration and temperature on the NO emission characteristics of turbulent, non-premixed methane (CH4)/ammonia (NH3)/air swirl flames in two-stage combustors at high pressure. Emission data were obtained using large-eddy simulations with a finite-rate chemistry method from model flames based on the energy fraction of NH3 (ENH3) in CH4/NH3 mixtures. Although NO emissions at the combustor exit were found to be significantly higher than those generated by CH4/air and NH3/air flames under both lean and stoichiometric primary zone conditions, these emissions could be lowered to approximately 300 ppm by employing far-rich equivalence ratios (?) of 1.3 to 1.4 in the primary zone. This effect was possibly due to the lower OH concentrations under far-rich conditions. An analysis of local flame characteristics using a newly developed mixture fraction equation for CH4/NH3/air flames indicated that the local temperature and NO and OH concentration distributions with local ? were qualitatively similar to those in NH3/air flames. That is, the maximum local NO and OH concentrations appeared at local ? of 0.9, although the maximum temperature was observed at local ? of 1.0. Both the temperature and OH concentration were found to gradually decrease with the partial replacement of CH4 with NH3. Consequently, NO emissions from CH4/NH3 flames were maximized at ENH3 in the range of 20% to 30%, after which the emissions decreased. Above 2100 K, the NO emissions from CH4/NH3 flames increased exponentially with temperature, which was not observed in NH3/air flames because of the lower flame temperatures in the latter. But, the maximum NO concentration in CH4/NH3 flames was occurred at a temperature slightly below the maximum temperature, just as in NH3/air flames. The apparent exponential increase in NO emissions from CH4/NH3 flames is attributed to a similar trend in the OH concentration at high temperatures.  相似文献   
2.
Kobayashi  M.  Zhang  Y.  Ishikawa  H.  Sun  J.  Oddershede  J.  Juul Jensen  D.  Miura  H. 《Experimental Mechanics》2021,61(5):817-828
Experimental Mechanics - The internal strain distribution developing during plastic deformation is important for understanding the mechanical properties of polycrystalline materials. Such...  相似文献   
3.
Algebras and Representation Theory - We study syzygies of (maximal) Cohen–Macaulay modules over one dimensional Cohen–Macaulay local rings. We assume that rings are generically...  相似文献   
4.
A new H-bonded crystal [RuIII(Him)3(Im)3] with three imidazole (Him) and three imidazolate (Im) groups was prepared to obtain a higher-temperature proton conductor than a Nafion membrane with water driving. The crystal is constructed by complementary N−H⋅⋅⋅N H-bonds between the RuIII complexes and has a rare Icy-c* cubic network topology with a twofold interpenetration without crystal anisotropy. The crystals show a proton conductivity of 3.08×10−5 S cm−1 at 450 K and a faster conductivity than those formed by only HIms. The high proton conductivity is attributed to not only molecular rotations and hopping motions of HIm frameworks that are activated at ∼113 K, but also isotropic whole-molecule rotation of [RuIII(Him)3(Im)3] at temperatures greater than 420 K. The latter rotation was confirmed by solid-state 2H NMR spectroscopy; probable proton conduction routes were predicted and theoretically considered.  相似文献   
5.
Several base-stabilized silyliumylidene ions ( 2 and 3 ) with different ligands were synthesized. Their behaviour appeared strongly dependent on the nature of ligand. Indeed, in contrast to the poorly reactive silyliumylidene ions 3 c,d stabilized by strongly donating ligands (DMAP, NHC), the silylene- and sulfide-supported one ( 2-H and 3 a ) exhibits higher reactivity toward various small molecules. Furthermore, their capability to successively activate multiple small molecules was clearly demonstrated by processes involving successive reactions with silane/formamide, CO2 and H2. Moreover, HBPin adduct of 3 a ( 8-C ) catalyzes the hydroboration of pyridine. Of particular interest, silylene-supported silyliumylidene complex 2-H is one of the rare species able to activate two H2 molecules.  相似文献   
6.
The development of nanostructured semiconductor electrodes represented by a mesoporous TiO2 nanocrystalline (mp-TiO2) film is currently bringing great progresses in photoelectrochemical (PEC) devices for solar-to-electricity and solar-to-chemical conversion. Two serious losses can occur in PEC devices: 1) recombination between the conduction band (CB) electrons and valence band (VB) holes in the bulk and at the surface and 2) back reaction or electron trapping by oxidant in the electrolyte solution during transport to the electron-collecting electrode. Thus, the major challenge in common with the nanostructured semiconductor photoanodes is to achieve efficient charge separation and electron transport. In this study, an ultrathin SiOx layer was formed on both the external and the internal surface of mp-TiO2 using an original chemisorption-calcination technique employing 1,3,5,7-tetramethyltetrasiloxane as a starting material. The SiOx surface modification of the mp-TiO2 photoanode drastically prolongs the mean lifetime of CB-electrons in TiO2 because of enhanced charge separation and electron transport by the negative charge applied in aqueous electrolyte solution. We have demonstrated that the performance of a one-compartment H2O2-photofuel cell using mp-TiO2 as the photoanode is greatly boosted by the surface modification with the SiOx layer. We anticipate that this methodology is widely applicable to nanostructured metal oxide semiconductor electrodes, contributing to the improvement in the performance of PEC devices.  相似文献   
7.
Journal of Radioanalytical and Nuclear Chemistry - Extraction chromatography flow-sheet employing octyl(phenyl)-N,N-diisobutylcarbonoylmethylphosphine oxide and bis(2-ethylhexyl) hydrogen phosphate...  相似文献   
8.
Ru is an important catalyst in many types of reactions. Specifically, Ru is well known as the best monometallic catalyst for oxidation of carbon monoxide (CO) and has been practically used in residential fuel cell systems. However, Ru is a minor metal, and the supply risk often causes violent fluctuations in the price of Ru. Performance‐improved and cost‐reduced solid‐solution alloy nanoparticles of the Cu‐Ru system for CO oxidation are now presented. Over the whole composition range, all of the CuxRu1?x nanoparticles exhibit significantly enhanced CO oxidation activities, even at 70 at % of inexpensive Cu, compared to Ru nanoparticles. Only 5 at % replacement of Ru with Cu provided much better CO oxidation activity, and the maximum activity was achieved by 20 at % replacement of Ru by Cu. The origin of the high catalytic performance was found as CO site change by Cu substitution, which was investigated using in situ Fourier transform infrared spectra and theoretical calculations.  相似文献   
9.
The direct 2‐deoxyglycosylation of nucleophiles with glycals leads to biologically and pharmacologically important 2‐deoxysugar compounds. Although the direct addition of hydroxyl and sulfonamide groups have been well developed, the direct 2‐deoxyglycosylation of amide groups has not been reported to date. Herein, we show the first direct 2‐deoxyglycosylation of amide groups using a newly designed Brønsted acid catalyst under mild conditions. Through mechanistic investigations, we discovered that the amide group can inhibit acid catalysts, and the inhibition has made the 2‐deoxyglycosylation reaction difficult. Diffusion‐ordered two‐dimensional NMR spectroscopy analysis implied that the 2‐chloroazolium salt catalyst was less likely to form aggregates with amides in comparison to other acid catalysts. The chlorine atom and the extended π‐scaffold of the catalyst played a crucial role for this phenomenon. This relative insusceptibility to inhibition by amides is more responsible for the catalytic activity than the strength of the acidity.  相似文献   
10.
This new method overcomes problems of conventional analytical methodologies such as light scattering and sampling reproducibility issues. We used this method for mechanistic studies of catalytic reactions under heterogeneous conditions. Direct-type hydroxymethylation reactions and Mukaiyama-type hydroxymethylation reactions both catalyzed by a scandium–bipyridine ligand complex under micellar conditions were employed as examples of heterogeneous reactions. For direct-type hydroxymethylation reactions, initial reaction rate assays revealed first-order dependency on both substrate and catalyst. On the other hand, Mukaiyama-type hydroxymethylation reactions showed first-order rate dependency on substrate, zero-order on catalyst and saturation kinetics on formaldehyde.

A direct and quantitative method for monitoring heterogeneous organic reactions has been developed by using direct analysis in real time mass spectrometry (DART-MS) with an isotope-labeled reaction product as an internal standard.  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