全文获取类型
收费全文 | 5267篇 |
免费 | 953篇 |
国内免费 | 763篇 |
专业分类
化学 | 4028篇 |
晶体学 | 69篇 |
力学 | 428篇 |
综合类 | 66篇 |
数学 | 559篇 |
物理学 | 1833篇 |
出版年
2024年 | 12篇 |
2023年 | 110篇 |
2022年 | 173篇 |
2021年 | 212篇 |
2020年 | 277篇 |
2019年 | 238篇 |
2018年 | 201篇 |
2017年 | 214篇 |
2016年 | 269篇 |
2015年 | 296篇 |
2014年 | 354篇 |
2013年 | 406篇 |
2012年 | 498篇 |
2011年 | 514篇 |
2010年 | 353篇 |
2009年 | 362篇 |
2008年 | 328篇 |
2007年 | 264篇 |
2006年 | 240篇 |
2005年 | 223篇 |
2004年 | 199篇 |
2003年 | 163篇 |
2002年 | 169篇 |
2001年 | 172篇 |
2000年 | 105篇 |
1999年 | 109篇 |
1998年 | 90篇 |
1997年 | 65篇 |
1996年 | 82篇 |
1995年 | 47篇 |
1994年 | 62篇 |
1993年 | 34篇 |
1992年 | 24篇 |
1991年 | 24篇 |
1990年 | 18篇 |
1989年 | 12篇 |
1988年 | 15篇 |
1987年 | 8篇 |
1986年 | 14篇 |
1985年 | 7篇 |
1984年 | 2篇 |
1983年 | 4篇 |
1982年 | 8篇 |
1981年 | 2篇 |
1980年 | 3篇 |
1975年 | 1篇 |
排序方式: 共有6983条查询结果,搜索用时 15 毫秒
151.
The grafting of ethylene glycol dimethacrylate (EGDMA) onto silk in aqueous alcohol systems using potassiumpersulfate (KPS) in the presence of air was investigated. Effects of grafting conditions, such as concentrations of monomer,initiator and formic acid, temperature and time, on the graft yield were determined. The optimum graft conditions were foundto be: T = 80℃, t = 30 min, [KPS] = 1.85% [on the weight ofmonomer (owm)]; [formic acid] = 0.2% (V/V); [EGDMA] =80% [on the weight of fiber (owf)]. The activation energy of grafting at 50-80℃ was found to be 71.31 kJ/mol for EGDMA.Grafting equations were also evaluated. The graft yield value can be regulated by the concentration of monomer. The graftcopolymerization of EGDMA onto silk is effective in improving the crease-proofing of silk fabrics. 相似文献
152.
Jie Hu Haoshan Hao Changping Chen Delin Yang Xing Hu 《Journal of membrane science》2006,280(1-2):809-814
The oxygen permeation properties of mixed-conducting ceramics SrFeCo0.5O3−δ (SFCO), Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCFO), La0.2Sr0.8Co0.8Fe0.2O3−δ (LSCFO) and Ba0.95Ca0.05Co0.8Fe0.2O3−δ (BCCFO) were studied by thermogravimetric method in the temperature range 600–900 °C. The results show that the oxygen adsorption rate constants ka of all material are larger than oxygen desorption rate constants kd and both ka and kd are not strongly dependent on temperature in the studied temperature range. The oxygen vacancy contents δ(N2) and δ(O2) in nitrogen and oxygen and their difference Δδ = δ(N2) − δ(O2) play an important role in determining the temperature behavior of oxygen permeation flux JO2. 相似文献
153.
He J Nie A He M He X Yu Z Ye X Xing Q 《Rapid communications in mass spectrometry : RCM》2000,14(9):765-771
A series of cyclic esters, which are optically active as a consequence of their helical structures, were synthesized to investigate the relationships between their structures and their optical activities. This paper reports the electron impact fragmentation mechanisms of these six cyclic esters. Accurate mass measurements and mass analyzed ion kinetic energy spectrometry confirmed fragmentation patterns. The stability of the fragment ions has a great influence on the fragmentation pathways, but no correlation with the optical activity was found. 相似文献
154.
The title complex, [La(btec)1/2(H2btec)1/2 (H2O)]n (H4btec= 1, 2,4,5‐benzenetetracarboxylic acid) (1) was synthesized by the hydrothermal reaction of 1,2,4,5‐benzenetetracarboxylic dianhydride with La(NO3)3·6H2O in H2O, and crystallizes in the triclinic system, space group P‐1 with a = 0.64403(3) nm, b = 0.94500(4) nm, c = 0.96380(5) nm, a = 88.535(2)°, β = 100.314(2)°, γ = 76.6470(10)°, V = 1.60968(10) nm3, Z = 2, and final R = 0.0274, Rw = 0.0735. In 1, each La(m) ion is coordinated by eight oxygen atoms from six carboxylate groups and one coordinated water molecule. Two different coordination modes of H4btec were present in the structure, one of which contains two protonated carboxylate groups to balance the charge. 相似文献
155.
A highly-efficient preparative procedure for ( R, S )- and ( S, S)-pyrroHdine-2-carboxyHc acid 3,5-dioxa-4-boracyclohepta[2, 1-α ; 3,4-α′] dlnaphthalen-4-yl esters [ namely ( R, S )-BNBAP and (S, S )-BNBAP] is described and the crystal structure of (R, S )-BNBAP was obtained. The data indicate that ( R, S )-BNBAP is a spirocyclic inner borate salt with almost normal te-trahedral configuration. This structural form may be the basic reason for their high chemical, optical and thermodynamic sta-bility. 相似文献
156.
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
157.
Zilu Chen Huihui Xing Fupei Liang 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(12):m576-m578
In the title compound, [Mn(C5H2N2O4)(H2O)2]n, the MnII ion has a distorted octahedral geometry and the 4‐oxido‐2‐oxo‐1,2‐dihydropyrimidine‐5‐carboxylate (Hiso2−) anion acts as a μ3:η4‐bridging ligand. Two oxo O atoms from different Hiso2− ligands bridge two MnII ions, forming centrosymmetric dinuclear building blocks. Each dinuclear building block interacts with another four by the coordination of the oxide groups and carboxylate O atoms, producing a two‐dimensional framework in the ab plane. Hydrogen bonds further extend the two‐dimensional sheets into a three‐dimensional supramolecular framework. 相似文献
158.
Solid phase microextraction (SPME) then capillary gas chromatography with mass spectrometric detection have been used for determination of nine phenyl compounds in snow water in Beijing City. Headspace extraction with a fiber coated with 100 µm PDMS was used to extract the compounds. Extraction and desorption times were optimized at 8 and 2 min, respectively. Relative standard deviation (RSD) of the analytical method was found to be less than 5%. The linear range was wide and limits of detection were less than 5 ng mL−1 for the nine target analytes. Several phenyl compounds at ng mL−1 levels were detected in snow samples in Beijing, indicating the corresponding air pollution. 相似文献
159.
160.
Xing Chen Wenguang Zhao Feng Wang Jie Xu .Dalian National Laboratory for Clean Energy State 《天然气化学杂志》2012,(5):481-487
Preparation of dispersed transition metal oxides catalyst with low oxidation state still remains a challenging task in heterogeneous catalysis.In this study,vanadium oxides supported on zeolite SBA-15 have been prepared under hydrothermal condition using V 2 O 5 and oxalic acid as sources of vanadium and reductant,respectively.The structures of samples,especially the oxidation state of vanadium,and the surface distribution of vanadium oxide species,have been thoroughly characterized using various techniques,including N 2-physisorption,X-ray diffraction(XRD),transmission electron microscopy(TEM),X-ray photoelectron spectroscopy(XPS),UV-visible spectra(UV-Vis) and UV-visible-near infrared spectra(UV-Vis-NIR).It is found that the majority of supported vanadium was in the form of vanadium(IV) oxide species with the low valence of vanadium.By adjusting hydrothermal treatment time,the surface distribution of vanadium(IV) oxide species can be tuned from vanadium(IV) oxide cluster to crystallites.These materials have been tested in the hydroxylation of benzene to phenol in liquid-phase with molecular oxygen in the absence of reductant.The catalyst exhibits high selectivity for phenol(61%) at benzene conversion of 4.6%,which is a relatively good result in comparison with other studies employing molecular oxygen as the oxidant. 相似文献