全文获取类型
收费全文 | 2349篇 |
免费 | 379篇 |
国内免费 | 752篇 |
专业分类
化学 | 3357篇 |
晶体学 | 5篇 |
力学 | 5篇 |
综合类 | 15篇 |
物理学 | 98篇 |
出版年
2024年 | 2篇 |
2023年 | 45篇 |
2022年 | 53篇 |
2021年 | 88篇 |
2020年 | 144篇 |
2019年 | 130篇 |
2018年 | 104篇 |
2017年 | 88篇 |
2016年 | 136篇 |
2015年 | 147篇 |
2014年 | 170篇 |
2013年 | 238篇 |
2012年 | 172篇 |
2011年 | 202篇 |
2010年 | 120篇 |
2009年 | 128篇 |
2008年 | 153篇 |
2007年 | 158篇 |
2006年 | 180篇 |
2005年 | 128篇 |
2004年 | 127篇 |
2003年 | 123篇 |
2002年 | 80篇 |
2001年 | 73篇 |
2000年 | 60篇 |
1999年 | 73篇 |
1998年 | 56篇 |
1997年 | 49篇 |
1996年 | 54篇 |
1995年 | 42篇 |
1994年 | 27篇 |
1993年 | 31篇 |
1992年 | 30篇 |
1991年 | 12篇 |
1990年 | 13篇 |
1989年 | 4篇 |
1988年 | 8篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1985年 | 10篇 |
1984年 | 7篇 |
1983年 | 2篇 |
1982年 | 3篇 |
1981年 | 1篇 |
1979年 | 2篇 |
1977年 | 1篇 |
1976年 | 2篇 |
1974年 | 1篇 |
1971年 | 1篇 |
排序方式: 共有3480条查询结果,搜索用时 125 毫秒
1.
Hydrogenation of acetophenone over nano‐Cu/SiO2 catalysts was investigated. The catalysts, prepared by a liquid precipitation method using various precipitating agents, were characterized using low‐temperature nitrogen adsorption, X‐ray diffraction, temperature‐programmed desorption of ammonia, hydrogen temperature‐programmed reduction, transmission electron microscopy and X‐ray photoelectron spectroscopy. It was found that the catalysts prepared by a homogeneous precipitation method had better activity and stability than those prepared by a co‐precipitation method. The catalyst prepared using urea as precipitating agent had well‐dispersed copper species, high surface area and abundant pore structure. The catalytic performance and mechanism of the Cu/SiO2 catalysts were further studied. It was found that the activity and stability of the catalysts could be improved by adjusting the proportion of Cu+/(Cu+ + Cu0). The sample prepared using urea as precipitating agent presented higher activity and selectivity. Also, the catalyst prepared using urea maintained a high catalytic performance while being continuously used for 150 h under the optimal reaction conditions. 相似文献
2.
Jared P. Klein Richard A. Register 《Journal of Polymer Science.Polymer Physics》2019,57(18):1188-1195
Hydrogenated polynorbornene (hPN) synthesized by ring‐opening metathesis polymerization (ROMP) exhibits a thermoreversible change in crystal polymorph at a temperature T cc below its melting point, T m. The polymorphic transition corresponds to a sharp increase in rotational disorder around the chain axis as the temperature is increased above T cc. Saturation of ROMP polynorbornene (PN) to hPN can be achieved through both catalytic and noncatalytic approaches. Here, three different hydrogenation routes were employed on the same precursor polymer: catalytic routes over either supported Pd0 or a Ni/Al complex, and noncatalytic saturation with diimide. The different hydrogenation routes result in hPNs with varying degrees of epimerization of the cyclopentylene ring (from cis to trans); these epimerized units are included in the hPN crystals. The crystal structure of the rotationally ordered hPN polymorph, observed below T cc, changes sharply at low levels of epimerization and then is weakly influenced by further increases in trans content. The stability of the rotationally ordered hPN polymorph decreases with increasing epimerization, as reflected in a reduction of T cc from 134 °C to 92 °C at 22% epimerization. T cc is less affected by epimerization than by the inclusion of a similar content of 5‐methylnorbornene units, reflecting the smaller size of the trans defect. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1188–1195 相似文献
3.
Xiaomin Ren Miao Guo He Li Chengbin Li Liang Yu Jian Liu Qihua Yang 《Angewandte Chemie (International ed. in English)》2019,58(41):14392-14392
4.
Back Cover: Single‐Atom Gold Catalysis in the Context of Developments in Parahydrogen‐Induced Polarization (Chem. Eur. J. 19/2015) 下载免费PDF全文
5.
Cover Picture: Ultrathin Coating of Confined Pt Nanocatalysts by Atomic Layer Deposition for Enhanced Catalytic Performance in Hydrogenation Reactions (Chem. Eur. J. 25/2016) 下载免费PDF全文
6.
Bio‐Inspired Transition Metal–Organic Hydride Conjugates for Catalysis of Transfer Hydrogenation: Experiment and Theory 下载免费PDF全文
Alex McSkimming Dr. Bun Chan Dr. Mohan M. Bhadbhade Dr. Graham E. Ball Prof. Stephen B. Colbran 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(7):2821-2834
Taking inspiration from yeast alcohol dehydrogenase (yADH), a benzimidazolium (BI+) organic hydride‐acceptor domain has been coupled with a 1,10‐phenanthroline (phen) metal‐binding domain to afford a novel multifunctional ligand ( L BI+) with hydride‐carrier capacity ( L BI++H?? L BIH). Complexes of the type [Cp*M( L BI)Cl][PF6]2 (M=Rh, Ir) have been made and fully characterised by cyclic voltammetry, UV/Vis spectroelectrochemistry, and, for the IrIII congener, X‐ray crystallography. [Cp*Rh( L BI)Cl][PF6]2 catalyses the transfer hydrogenation of imines by formate ion in very goods yield under conditions where the corresponding [Cp*Ir( L BI)Cl][PF6] and [Cp*M(phen)Cl][PF6] (M=Rh, Ir) complexes are almost inert as catalysts. Possible alternatives for the catalysis pathway are canvassed, and the free energies of intermediates and transition states determined by DFT calculations. The DFT study supports a mechanism involving formate‐driven Rh?H formation (90 kJ mol?1 free‐energy barrier), transfer of hydride between the Rh and BI+ centres to generate a tethered benzimidazoline (BIH) hydride donor, binding of imine substrate at Rh, back‐transfer of hydride from the BIH organic hydride donor to the Rh‐activated imine substrate (89 kJ mol?1 barrier), and exergonic protonation of the metal‐bound amide by formic acid with release of amine product to close the catalytic cycle. Parallels with the mechanism of biological hydride transfer in yADH are discussed. 相似文献
7.
Edward A. Karakhanov Anton L. Maximov Anna V. Zolotukhina Nadezhda Yatmanova Edward Rosenberg 《应用有机金属化学》2015,29(11):777-784
A series of Pd–Ag mixed‐metal nanocatalysts were prepared by reduction of Pd–Ag salts in the presence of poly(propylene imine) dendrimers, which were covalently bound to the surface of a silica polyamine composite, BP‐1 (polyallylamine covalently bound to a silanized amorphous silica gel). Three different Pd‐to‐Ag ratios were evaluated (50:50, catalyst 1 ; 40:60, catalyst 2 ; 60:40, catalyst 3 ) with the goal of determining how the amount of Ag effects selectivity, rate and conversion in the selective reduction of alkynes, such as phenylacetylene and 1‐ or 4‐octyne, to the corresponding alkenes. Conditions for the catalysis are reported where there is improved selectivity without a serious reduction in rate when compared with the analogous Pd‐only catalysts. Catalyst 2 worked best for phenylacetylene and catalyst 3 worked best for the octynes. The catalysts could be reused seven times without loss of activity. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
8.
Inside Cover: Bio‐Inspired Transition Metal–Organic Hydride Conjugates for Catalysis of Transfer Hydrogenation: Experiment and Theory (Chem. Eur. J. 7/2015) 下载免费PDF全文
9.
Single‐Atom Gold Catalysis in the Context of Developments in Parahydrogen‐Induced Polarization 下载免费PDF全文
Prof. Avelino Corma Oleg G. Salnikov Danila A. Barskiy Dr. Kirill V. Kovtunov Prof. Igor V. Koptyug 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(19):7012-7015
A highly isolated monoatomic gold catalyst, with single gold atoms dispersed on multiwalled carbon nanotubes (MWCNTs), has been synthesized, characterized, and tested in heterogeneous hydrogenation of 1,3‐butadiene and 1‐butyne with parahydrogen to maximize the polarization level and the contribution of the pairwise hydrogen addition route. The Au/MWCNTs catalyst was found to be active and efficient in pairwise hydrogen addition and the estimated contributions from the pairwise hydrogen addition route are at least an order of magnitude higher than those for supported metal nanoparticle catalysts. Therefore, the use of the highly isolated monoatomic catalysts is very promising for production of hyperpolarized fluids that can be used for the significant enhancement of NMR signals. A mechanism of 1,3‐butadiene hydrogenation with parahydrogen over the highly isolated monoatomic Au/MWCNTs catalyst is also proposed. 相似文献
10.
催化裂化是石油化工的核心单元之一.从催化裂化尾气中分离出来的碳四馏分富含许多的不饱和烯烃,如1-丁烯、顺、反式-2-丁烯以及少量的1,3-丁二烯,这些不饱和烯烃可以通过后续聚合反应,生成合成橡胶和工程塑料的重要原料,具有重要的应用价值.上述工艺过程对原料中1,3-丁二烯的含量(<100~200 ppm)有严苛的要求.采用选择性加氢技术对碳四馏分中的1,3-丁二烯进行选择性加氢,将其转化为更高附加值的单烯烃是一个理想的解决方案.然而,1,3-丁二烯加氢反应得到的单烯烃可能发生深度加氢得到副产物丁烷.因此,开发高效选择性加氢催化剂对碳四资源的利用具有重要的现实意义.另一方面,1,3-丁二烯加氢反应可以作为模型反应,用来考察选择性加氢催化剂的性能.基于此,该反应无论在工业界还是学术界均受到广泛关注.尽管如此,有关1,3-丁二烯加氢催化剂研究进展方面的综述极少.仅有关于1,3-丁二烯加氢作为模型反应的综述报道.本文对过去半个世纪以来1,3-丁二烯加氢反应中不同催化剂的发展历程进行系统综述,特别是包括Pd,Pt和Au等的单一贵金属催化剂.重点介绍以下内容:(1)固体催化剂构效关系,包括活性金属尺寸效应、晶面和形貌效应以及载体效应(晶相、孔道和酸碱性);(2)高性能催化剂的设计新策略,如单原子催化剂、核壳结构催化剂、金属-离子液复合催化体系以及载体的形貌调控;(3)催化剂的反应机理和失活机理.提出了1,3-丁二烯选择性加氢高性能催化剂开发面临的挑战,并对潜在的发展方向进行了展望.本文认为随着纳米技术和金属纳米材料合成方法的快速发展,对贵金属活性组分进行原子层面上的调控(包括形貌、尺寸以及单原子配位环境等)已成为可能.这将有助于研制出一类新型高性能选择性加氢催化材料,从而实现高转化率条件下高附加值单烯烃的定向转化.此外,载体的酸碱性和孔道结构的调控有助于进一步调节催化剂的抗积炭性能,也是未来发展的一个重要方向. 相似文献