全文获取类型
收费全文 | 8475篇 |
免费 | 1523篇 |
国内免费 | 959篇 |
专业分类
化学 | 6297篇 |
晶体学 | 76篇 |
力学 | 499篇 |
综合类 | 45篇 |
数学 | 1055篇 |
物理学 | 2985篇 |
出版年
2024年 | 16篇 |
2023年 | 203篇 |
2022年 | 301篇 |
2021年 | 322篇 |
2020年 | 457篇 |
2019年 | 391篇 |
2018年 | 345篇 |
2017年 | 277篇 |
2016年 | 405篇 |
2015年 | 416篇 |
2014年 | 510篇 |
2013年 | 626篇 |
2012年 | 766篇 |
2011年 | 823篇 |
2010年 | 548篇 |
2009年 | 489篇 |
2008年 | 480篇 |
2007年 | 454篇 |
2006年 | 471篇 |
2005年 | 356篇 |
2004年 | 278篇 |
2003年 | 227篇 |
2002年 | 279篇 |
2001年 | 160篇 |
2000年 | 169篇 |
1999年 | 179篇 |
1998年 | 129篇 |
1997年 | 128篇 |
1996年 | 139篇 |
1995年 | 108篇 |
1994年 | 97篇 |
1993年 | 64篇 |
1992年 | 66篇 |
1991年 | 57篇 |
1990年 | 46篇 |
1989年 | 42篇 |
1988年 | 37篇 |
1987年 | 18篇 |
1986年 | 25篇 |
1985年 | 21篇 |
1984年 | 12篇 |
1983年 | 3篇 |
1982年 | 1篇 |
1981年 | 6篇 |
1980年 | 1篇 |
1957年 | 3篇 |
1935年 | 1篇 |
1931年 | 1篇 |
1930年 | 3篇 |
1922年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 78 毫秒
251.
[structure: see text] The viability of the Diels-Alder (DA) cycloaddition of conjugated dienes onto the sidewalls of single-wall carbon nanotubes is assessed by means of a two-layered ONIOM(B3LYP/6-31G:AM1) approach. Whereas the DA reaction of 1,3-butadiene on the sidewall of an armchair (5,5) nanotube is found to be unfavorable, the cycloaddition of quinodimethane is predicted to be viable due to the aromaticity stabilization at the corresponding transition states and products. 相似文献
252.
253.
Xianpeng Yin Hao Dong Shiqiang Wang Yun Liang Ning Gao Wanlin Zhang Li Tian Fuwei Sun Guangtao Li 《中国化学快报》2019,30(1):179-182
In this work, large area gold-nanoparticle-cluster pillar array with a gold mirror as high-performance SERS substrate was facilely fabricated by combined use of nanosphere lithography and self-assembly approach. 相似文献
254.
P. L. Liu J. L. Tian R. E. Jervis Y. Q. Li 《Journal of Radioanalytical and Nuclear Chemistry》1997,217(1):39-43
A total of 29 major and trace elements have been determined in 43 plant samples collected from the Xizang (Tibet) Plateau using INAA at a SLOWPOKE mini-reactor in order to study elemental background concentration values in Xizang plants. In this paper are reported elemental concentrations of different parts of the plants compared to average values of plants worldwide. The preliminary results suggest that nutritional, plant elements in this region are quite low indicative of a state of malnutrition, while the contents of Al, Ti, Cr and Ba are comparatively high. These findings indicate that the concentrations of most elements in the plants are mainly affected by local soil geochemical characteristics. Some variation in elemental distribution within the plants was also evident: in general, higher concentrations were found in stems compared to roots, and, differences for nutritional elements among the plant species were much greater than found for other elements. 相似文献
255.
Surface-enhanced Raman scattering in the ultraviolet spectral region: UV-SERS on rhodium and ruthenium electrodes 总被引:3,自引:0,他引:3
Ren B Lin XF Yang ZL Liu GK Aroca RF Mao BW Tian ZQ 《Journal of the American Chemical Society》2003,125(32):9598-9599
We report the first observation of surface-enhanced Raman scattering (SERS) excited with ultraviolet (UV) light from transition metal electrodes. Adsorbed pyridine and SCN- on rough rhodium (Rh) and ruthenium (Ru) electrodes, respectively, have been studied using 325 nm laser excitation. In contrast, the best enhancers in the visible and near infrared, silver and gold, do not produce UV-SERS. The experimental data of UV-SERS are in agreement with our preliminary theoretical calculation based on the electromagnetic enhancement mechanism. The enhancement factor is about 2 orders of magnitude for the Rh and Ru electrodes when they are excited at 325 nm. 相似文献
256.
Zhang B Li JF Zhong QL Ren B Tian ZQ Zou SZ 《Langmuir : the ACS journal of surfaces and colloids》2005,21(16):7449-7455
Core-shell Au-Pt nanoparticles were synthesized by using a seed growth method and characterized by transmission electron microscopy, X-ray diffraction, and UV-vis spectroscopy. Au(core)-Pt(shell)/GC electrodes were prepared by drop-coating the nanoparticles on clean glassy carbon (GC) surfaces, and their electrochemical behavior in 0.5 M H2SO4 revealed that coating of the Au core by the Pt shell is complete. The electrooxidation of carbon monoxide and methanol on the Au(core)-Pt(shell)/GC was also examined, and the results are similar to those obtained on a bulk Pt electrode. High quality surface-enhanced Raman scattering (SERS) spectra of both adsorbed CO and thiocyanate were observed on the Au(core)-Pt(shell)/GC electrodes. The potential-dependent SERS features resemble those obtained on electrochemically roughened bulk Pt or Pt thin films deposited on roughened Au electrodes. For thiocyanate, the C-N stretching frequency increases with the applied potential, yielding two distinctly different dnu(CN)/dE. From -0.8 to -0.2 V, the dnu(CN)/dE is ca. 50 cm(-1)/V, whereas it is 90 cm(-1)/V above 0 V. The bandwidth along with the band intensity increases sharply above 0 V. At the low-frequency region, Pt-NCS stretching mode at 350 cm(-1) was observed at the potentials from -0.8 to 0 V, whereas the Pt-SCN mode at 280 cm(-1) was largely absent until around 0 V and became dominant at more positive potentials. These potential-dependent spectral transitions were attributed to the adsorption orientation switch from N-bound dominant at the negative potential region to S-bound at more positive potentials. The origin of the SERS activity of the particles is briefly discussed. The study demonstrates a new method of obtaining high quality SERS on Pt-group transition metals, with the possibility of tuning SERS activity by varying the core size and the shell thickness. 相似文献
257.
Hui Yang Xing Chen Guoxiang Hu Wan-Ting Chen Siobhan J. Bradley Weijie Zhang Gaurav Verma Thomas Nann De-en Jiang Paul E. Kruger Xiangke Wang He Tian Geoffrey I. N. Waterhouse Shane G. Telfer Shengqian Ma 《Chemical science》2020,11(13):3523
Optimizing interfacial contacts and thus electron transfer phenomena in heterogeneous electrocatalysts is an effective approach for enhancing electrocatalytic performance. Herein, we successfully synthesized ultrafine β-Mo2C nanoparticles confined within hollow capsules of nitrogen-doped porous carbon (β-Mo2C@NPCC) and found that the surface layer of molybdenum atoms was further oxidized to a single Mo–O surface layer, thus producing intimate O–Mo–C interfaces. An arsenal of complementary technologies, including XPS, atomic-resolution HAADF-STEM, and XAS analysis clearly reveals the existence of O–Mo–C interfaces for these surface-engineered ultrafine nanostructures. The β-Mo2C@NPCC electrocatalyst exhibited excellent electrocatalytic activity for the hydrogen evolution reaction (HER) in water. Theoretical studies indicate that the highly accessible ultrathin O–Mo–C interfaces serving as the active sites are crucial to the HER performance and underpinned the outstanding electrocatalytic performance of β-Mo2C@NPCC. This proof-of-concept study opens a new avenue for the fabrication of highly efficient catalysts for HER and other applications, whilst further demonstrating the importance of exposed interfaces and interfacial contacts in efficient electrocatalysis.Ultrafine β-Mo2C nanostructures encapsulated in N-doped carbon capsules featuring O–Mo–C interfaces as the active sites for HER have been unveiled. 相似文献
258.
A vanadium oxide-modified glassy carbon electrode was simply and conveniently fabricated by casting vanadium tri(isoproxide) oxide (VO(OC3H7)3) and poly(propylene carbonate) (PPC) onto the glassy carbon electrode surface. The electrochemical properties of iodide at the VO(OC3H7)3-PPC film-modified glassy carbon electrode were investigated by cyclic voltammetry, and an anodic peak was observed at approximately +0.71 V (vs. SCE). Based on this, a sensitive and convenient electrochemical method was proposed for the determination of iodide. Flow injection amperometry (FIA) exhibited a good linear relationship with the concentration of iodide in the range of 5 × 10−7 mol L−1 and 1 × 10−3 mol L−1, and the detection limit was 1 × 10−7 mol L−1. Quantitative recovery of iodide in synthetic samples has been obtained and the interferences from different cations and anions have been studied. The method has been successfully applied to the determination of iodide in dry edible seaweed. The concentrations of iodide measured by this method are in good agreement with those obtained by spectrophotometric method. 相似文献
259.
C(2)-symmetric bis(oxazolinato)lanthanide complexes of the type [(4R,5S)-Ph(2)Box]La[N(TMS)(2)](2), [(4S,5R)-Ar(2)Box]La[N(TMS)(2)](2), and [(4S)-Ph-5,5-Me(2)Box]La[N(TMS)(2)](2) (Box = 2,2'-bis(2-oxazoline)methylenyl; Ar = 4-tert-butylphenyl, 1-naphthyl; TMS = SiMe(3)) serve as precatalysts for the efficient enantioselective intramolecular hydroamination/cyclization of aminoalkenes and aminodienes. These new catalyst systems are conveniently generated in situ from the known metal precursors Ln[N(TMS)(2)](3) or Ln[CH(TMS)(2)](3) (Ln = La, Nd, Sm, Y, Lu) and 1.2 equiv of commercially available or readily prepared bis(oxazoline) ligands such as (4R,5S)-Ph(2)BoxH, (4S,5R)-Ar(2)BoxH, and (4S)-Ph-5,5-Me(2)BoxH. The X-ray crystal structure of [(4S)-(t)BuBox]Lu[CH(TMS)(2)](2) provides insight into the structure of the in situ generated precatalyst species. Lanthanides having the largest ionic radii exhibit the highest turnover frequencies as well as enantioselectivities. Reaction rates maximize near 1:1 BoxH:Ln ratio (ligand acceleration); however, increasing the ratio to 2:1 BoxH:Ln decreases the reaction rate, while affording enantiomeric excesses similar to the 1:1 BoxH:Ln case. A screening study of bis(oxazoline) ligands reveals that aryl stereodirecting groups at the oxazoline ring 4 position and additional substitution (geminal dimethyl or aryl) at the 5 position are crucial for high turnover frequencies and good enantioselectivities. The optimized precatalyst, in situ generated [(4R,5S)-Ph(2)Box]La[N(TMS)(2)](2), exhibits good rates and enantioselectivities, comparable to or greater than those achieved with chiral C(1)-symmetric organolanthanocene catalysts, even for poorly responsive substrates (up to 67% ee at 23 degrees C). Kinetic studies reveal that hydroamination rates are zero order in [amine substrate] and first order in [catalyst], implicating the same general mechanism for organolanthanide-catalyzed hydroamination/cyclizations (intramolecular turnover-limiting olefin insertion followed by the rapid protonolysis of an Ln-C bond by amine substrate) and implying that the active catalytic species is monomeric. 相似文献
260.
Seed‐Mediated Synthesis of Gold Tetrahedra in High Purity and with Tunable,Well‐Controlled Sizes 下载免费PDF全文
Yiqun Zheng Wenying Liu Tian Lv Ming Luo Dr. Hefei Hu Dr. Ping Lu Dr. Sang‐Il Choi Chao Zhang Dr. Jing Tao Prof. Yimei Zhu Prof. Zhi‐Yuan Li Prof. Younan Xia 《化学:亚洲杂志》2014,9(9):2635-2640
We report a facile synthesis of Au tetrahedra in high purity and with tunable, well‐controlled sizes via seed‐mediated growth. The success of this synthesis relies on the use of single‐crystal, spherical Au nanocrystals as the seeds and manipulation of the reaction kinetics to induce an unsymmetrical growth pattern for the seeds. In particular, the dropwise addition of a precursor solution with a syringe pump, assisted by cetyltrimethylammonium chloride and bromide at appropriate concentrations, was found to be critical to the formation of Au tetrahedra in high purity. Their sizes could be readily tuned in the range of 30–60 nm by simply varying the amount of precursor added to the reaction solution. The current strategy not only enables the synthesis of Au tetrahedra with tunable and controlled sizes but also provides a facile and versatile approach to reducing the symmetry of nanocrystals made of a face‐centered cubic lattice. 相似文献