全文获取类型
收费全文 | 1555篇 |
免费 | 165篇 |
国内免费 | 719篇 |
专业分类
化学 | 1723篇 |
晶体学 | 3篇 |
力学 | 88篇 |
综合类 | 11篇 |
数学 | 114篇 |
物理学 | 45篇 |
综合类 | 455篇 |
出版年
2024年 | 3篇 |
2023年 | 9篇 |
2022年 | 16篇 |
2021年 | 28篇 |
2020年 | 36篇 |
2019年 | 40篇 |
2018年 | 50篇 |
2017年 | 41篇 |
2016年 | 72篇 |
2015年 | 68篇 |
2014年 | 71篇 |
2013年 | 134篇 |
2012年 | 116篇 |
2011年 | 132篇 |
2010年 | 106篇 |
2009年 | 96篇 |
2008年 | 130篇 |
2007年 | 136篇 |
2006年 | 135篇 |
2005年 | 145篇 |
2004年 | 120篇 |
2003年 | 133篇 |
2002年 | 105篇 |
2001年 | 103篇 |
2000年 | 78篇 |
1999年 | 62篇 |
1998年 | 40篇 |
1997年 | 33篇 |
1996年 | 35篇 |
1995年 | 40篇 |
1994年 | 21篇 |
1993年 | 28篇 |
1992年 | 19篇 |
1991年 | 19篇 |
1990年 | 7篇 |
1989年 | 13篇 |
1988年 | 6篇 |
1987年 | 4篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1979年 | 1篇 |
1977年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有2439条查询结果,搜索用时 10 毫秒
21.
22.
溶胶凝胶法制氧化铝负载铜基超细粒子催化剂的研究 总被引:9,自引:1,他引:9
采用溶胶凝胶法制氧化铝负载铜基超细粒子催化剂的制备了氧化铝负载的铜基超细粒子催化剂,用TG-DTA,XRD,BET以及TEM等技术手段,对催化剂的物相结构,表面孔结构,粒子形貌以及催化性能等进行了研究。结果表明,利用溶胶凝胶法,可以直接帛备出高比表面积,低堆积密度的纤维状纳米级负载型Cu/Al2O3超细粒子;活性组分以远低于纳米级的微晶粒子簇状态,均匀地分散在纳米级氧化铝载体表面上,而且在低于50 相似文献
23.
24.
The Incorporation of Titania into Modified Silicates for Solar Photodegradation of Aqueous Species 总被引:2,自引:0,他引:2
Lowell R. Matthews David Avnir Alexander D. Modestov Srinivasan Sampath Ovadia Lev 《Journal of Sol-Gel Science and Technology》1997,8(1-3):619-623
A new class of sol-gel-derived photocatalytic materials has been synthesized and used in solar-assisted photodegradation studies. The materials are comprised of a homogeneous dispersion of commercial TiO2 powder into silica and organically modified silicate (Ormosil) hosts. The efficiency of the photocatalytic properties of these TiO2-containing materials was determined by their relative performance in the solar photodecomposition of aqueous rhodamine B. The improved adsorption properties of the modified materials compared to commercial TiO2 increase the photodecomposition rate and the buoyancy properties, although excess hydrophobicity decreases the wetted section of the catalyst and its photocatalytic performance. These materials can be used as floatable catalysts for solar-assisted water purification. 相似文献
25.
V. I. Simagina V. V. Litvak I. V. Stoyanova V. A. Yakovlev V. M. Mastikhin I. V. Afanasenkova V. A. Likholobov 《Russian Chemical Bulletin》1996,45(6):1321-1324
Hydrodechlorination of chlorobcnzene by chemically bound hydrogen in the presence of transition metal compounds was studied. Alkali and alkaline earth metal hydrides (NaH, MgH2, LiAlH4, NaH(LiAlH4)/12) were used as the sources of the chemically bound hydrogen. The effect of the natures of the hydride and of the transition metal on the activity was studied under comparable conditions. The Pd/C-NaH(LiAlH41/2 catalytic system was found to be the most active. This system made it possible to perform the quantitative dechlorination of 2,3-dichlorodibenzo-p-dioxin at 70 °C.Deceased.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1391–1394, June, 1996. 相似文献
26.
茂锆载体催化剂下的乙烯/辛烯共聚及聚合物的^13C NMR研究 总被引:3,自引:0,他引:3
茂锆载体催化剂下的乙烯/辛烯共聚及聚合物的~(13)CNMR研究刘胜生,于广谦,黄葆同(中国科学院长春应用化学研究所长春130022)关键词茂锆载体催化剂,共聚,序列分布,~(13)CNMR由于茂锆催化剂具有高活性,单一活性中心等特点[1,2],并且能... 相似文献
27.
采用表面改性法制备了负载型Ni2(OEt)2/SiO2双核金属乙氧基配合物催化剂,利用示差量热、红外光谱和微反技术对催化剂的表面结构、热稳定性、化学吸附性质和催化活性进行了研究.结果表明,负载型双核金属乙氧基配合物Ni2(OEt)2/SiO2中的Ni2+与载体SiO2表面的O2-以双齿配位形式键合;二氧化碳在催化剂表面存在桥式吸附态和碳酸单乙酯基物种两种吸附态,丙烯则只有一种分子吸附态;在适宜的反应条件下,二氧化碳和丙烯在Ni2(OEt)2/SiO2催化剂上的反应产物主要是甲基丙烯酸.根据实验结果,提出了二氧化碳和丙烯在Ni2(OEt)2/SiO2催化剂表面的反应机理,反应物分子共吸附于催化剂表面同一活性单元上,羧酸根和丙烯解离吸附态的形成是反应顺利进行的关键步骤. 相似文献
28.
Geometries and stabilization energies of various simple H-bonded complexes (water dimer, hydrogen fluoride dimer, formamide
dimer, formic acid dimer) have been determined by a gradient optimization that eliminates the basis set superposition error
(BSSE) by the counterpoise (CP) method in each gradient cycle as well as by the standard gradient optimization. Both optimization
methods lead to different potential energy surfaces (PES). The difference depends on the theoretical level used and is larger
if correlation energy is considered. Intermolecular distances from the CP-corrected PES are consistently longer, and this
difference might be significant (∼0.1 ?); also angular characteristics determined from both surfaces differ significantly.
Different geometries were obtained even when passing to larger basis sets (aug-cc-pVDZ). The standard optimization procedure
can result in a completely wrong structure. For example, the “quasi-linear” structure of the (HF)2 (global minimum) does not exist at the standard MP2/ 6-31G** PES (where only cyclic structure was detected) and is found
only at the CP-corrected PES. Stabilization energies obtained from the CP-corrected PES are always larger than these from
the standard PES where the BSSE is added only a posteriori for the final optimized structure; both energies converge only
when passing to a larger basis set (aug-cc-pVDZ).
Received: 11 March 1998 / Accepted: 19 June 1998 / Published online: 4 September 1998
RID="
ID=" <E6>Acknowledgements.</E6> The project was supported by the Grant Agency of the Czech Republic (Grant No. 203/98/1166).
RID="
ID=" <E5>Correspondence to</E5>: P. Hobza 相似文献
29.
STUDY ON 1-HEXENE POLYMERIZATION BASED ON ZIEGLER-NATTA CATALYSTS WITH DOPED SUPPORT 总被引:1,自引:0,他引:1
XueJiang Zhi-qiangFan 《高分子科学》2004,(4):305-308
A series of Ti/Mg supported catalysts are prepared by using ball-milled mixtures of MgCl2-ethanol adducts and NaCl as supports, and 1-hexene polymerizations catalyzed by the novel catalysts are studied. It is found that the molecular weight distribution of poly(1-hexene) becomes apparently narrower when catalysts with doped supports are used, indicating that changing the structure of the support is an effective way to regulate the active center distribution of heterogeneous Ziegler-Natta catalyst. 相似文献
30.
Polypropylene (PP) has become an indispensable material in our daily lives. Annual worldwide production of PP is now more than 30000000 tons and is predicted to grow at an annual rate of about 6% during the first decade of the 21st century. Commercial production of PP began in 1957 with the use of TiCl(3) catalysts established by Ziegler and Natta. However, the low activities and low stereospecificities of the catalysts resulted in large amounts of catalyst residue and atactic PP in the product, necessitating steps for their removal in commercial production. As a means of finding appropriate catalysts, we developed MgCl(2)-supported TiCl(4) catalysts, which basic concept was introduction of organic compounds onto the inorganic crystal catalyst surface. This addition led to remarkable enhancements in stereospecificity with extremely high activity. Use of the new catalysts enlarged and simplified the PP production process by eliminating the steps previously required for removal of catalyst residue and atactic PP. In addition, it greatly improved the properties of the PP, enabling a much wider range of PP applications by replacing metal and engineering plastics with the highly stereoregular PP. Therefore, these catalysts helped the rapid establishment of the current PP industry and now play a major role in production. The latest MgCl(2)-supported TiCl(4) catalyst is providing precise control of the isotactic PP structure. Future expectations for this type of catalyst are to acquire a single-site nature and to contribute to the creation of a new class of hybrid materials. 相似文献