全文获取类型
收费全文 | 7261篇 |
免费 | 999篇 |
国内免费 | 2081篇 |
专业分类
化学 | 9325篇 |
晶体学 | 32篇 |
力学 | 71篇 |
综合类 | 59篇 |
数学 | 7篇 |
物理学 | 847篇 |
出版年
2024年 | 8篇 |
2023年 | 119篇 |
2022年 | 168篇 |
2021年 | 310篇 |
2020年 | 418篇 |
2019年 | 323篇 |
2018年 | 302篇 |
2017年 | 283篇 |
2016年 | 388篇 |
2015年 | 383篇 |
2014年 | 481篇 |
2013年 | 797篇 |
2012年 | 522篇 |
2011年 | 490篇 |
2010年 | 435篇 |
2009年 | 432篇 |
2008年 | 511篇 |
2007年 | 530篇 |
2006年 | 453篇 |
2005年 | 406篇 |
2004年 | 397篇 |
2003年 | 433篇 |
2002年 | 240篇 |
2001年 | 220篇 |
2000年 | 208篇 |
1999年 | 171篇 |
1998年 | 123篇 |
1997年 | 143篇 |
1996年 | 130篇 |
1995年 | 120篇 |
1994年 | 92篇 |
1993年 | 68篇 |
1992年 | 70篇 |
1991年 | 40篇 |
1990年 | 39篇 |
1989年 | 24篇 |
1988年 | 20篇 |
1987年 | 9篇 |
1986年 | 7篇 |
1985年 | 10篇 |
1984年 | 5篇 |
1983年 | 3篇 |
1982年 | 1篇 |
1981年 | 3篇 |
1980年 | 2篇 |
1977年 | 1篇 |
1973年 | 1篇 |
1969年 | 1篇 |
1959年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
11.
Wacker oxidation is an industry-adopted process to transform olefins into value-added epoxides and carbonyls. However, traditional Wacker oxidation involves the use of homogeneous palladium and copper catalysts for the olefin addition and reductive elimination. Here, we demonstrated an ultrahigh loading Cu single atom catalyst(14% Cu, mass fraction) for the palladium-free Wacker oxidation of 4-vinylanisole into the corresponding ketone with N-methylhydroxylamine hydrochloride as an additive under mild conditions. Mechanistic studies by 18O and deuterium isotope labelling revealed a hydrogen shift mechanism in this palladium-free process using N-methylhydroxylamine hydrochloride as the oxygen source. The reaction scope can be further extended to Kucherov oxidation. Our study paves the way to replace noble metal catalysts in the traditional homogeneous processes with single atom catalysts. 相似文献
12.
Shilin Jiang Dr. Yalan Liu Dr. Lin Wang Prof. Zhifang Chai Prof. Wei-Qun Shi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(60):e202201145
The coordination chemistry of f-block elements (lanthanide and actinide) in molten salts has become a resounding topic in view of its great importance to the research and development (R&D) of molten salt reactors and pyroprocessing. In this Review article, a general overview of the coordination chemistry of f-block elements in molten salts is provided including past achievements and recent advances. Particular emphases are placed on the oxidation state, speciation, and solution structure of f-block metal ions in molten salts, as well as their relationships with the salt composition. Furthermore, this review briefly discusses the spectroscopic and theoretical methods that complement each other in revealing the coordination properties. 相似文献
13.
Haruki Inoue Dr. Shin-ichi Naya Atsunobu Akita Dr. Hisashi Sugime Prof. Dr. Hiroaki Tada 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(46):e202201653
Gold nanoparticles with different mean sizes were formed on antimony-doped tin oxide nanocrystals by the temperature-varied deposition-precipitation method (Au/ATO NCs). Au/ATO NCs possess strong absorption in the near-infrared region due to Drude excitation in addition to the localized surface plasmon resonance (LSPR) of AuNPs around 530 nm. Au/ATO NCs show thermally activated catalytic activity for the oxidation of cinnamyl alcohol to cinnamaldehyde by hydrogen peroxide. The catalytic activity increases with a decrease in the mean Au particle size (dAu) at 5.3 nm≤dAu≤8.2 nm. Light irradiation (λex >660 nm, ∼0.5 sun) of Au/ATO NCs increases the rate of reaction by more than twice with ∼95 % selectivity. Kinetic analyses indicated that the striking enhancement of the reaction stems from the rise in the temperature near the catalyst surface of ∼30 K due to the photothermal effect of the ATO NCs. 相似文献
14.
The first-principles DFT calculations together with microkinetic analysis reveal the complex catalytic mechanism of low-content NO oxidation on CrO2(110) at room temperature. It quantitatively makes clear that CrO2(110) can exhibit considerable activity with the Mars-van-Krevelen mechanism preferred, and the nitrate species serves as the key poisoning species. 相似文献
15.
Three mesoporous molecular sieves loaded silicotungstic acids, named HSiW/SBA-15, HSiW/MCM-41, HSiW/MCM-48, were prepared and characterised by XRD, FT-IR, TEM and SEM. The catalytic performance of the prepared materials for the Baeyer-Villiger oxidation of cyclic ketones was carried out in the presence of 30%H2O2 under mild conditions. These loading materials were proved to be efficient and reusable catalysts, they all exhibited excellent catalytic performance for the Baeyer-Villiger oxidation of cyclic ketones with 30% H2O2 as oxidant. Many cyclic ketones were efficiently converted to the corresponding lactones with up to 90% conversions and high selectivities under the optimum reaction conditions. Cyclic ketones were efficiently oxidised by mesoporous materials sopported silicotungstic acid to the corresponding lactones with 30%H2O2 as oxidant. All of the catalysts showed promising recyclability in the reactions. 相似文献
16.
Kevin Salzmann Dr. Candela Segarra Prof. Dr. Martin Albrecht 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(23):9017-9021
An exceptionally efficient ruthenium-based catalyst for olefin oxidation has been designed by exploiting N,N′-bis(pyridylidene)oxalamide (bisPYA) as a donor-flexible ligand. The dynamic donor ability of the bisPYA ligand, imparted by variable zwitterionic and neutral resonance structure contributions, paired with the redox activity of ruthenium provided catalytic activity for Lemieux–Johnson-type oxidative cleavage of olefins to efficiently prepare ketones and aldehydes. The ruthenium bisPYA complex significantly outperforms state-of-the-art systems and displays extraordinary catalytic activity in this oxidation, reaching turnover frequencies of 650 000 h−1 and turnover numbers of several millions. 相似文献
17.
Daniel Josef Bell Monika Wiese Ariel Augusto Schönberger Matthias Wessling 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(37):16181-16187
Metal–organic frameworks (MOFs) are suitable enzyme immobilization matrices. Reported here is the in situ biomineralization of glucose oxidase (GOD) into MOF crystals (ZIF-8) by interfacial crystallization. This method is effective for the selective coating of porous polyethersulfone microfiltration hollow fibers on the shell side in a straightforward one-step process. MOF layers with a thickness of 8 μm were synthesized, and fluorescence microscopy and a colorimetric protein assay revealed the successful inclusion of GOD into the ZIF-8 layer with an enzyme concentration of 29±3 μg cm−2. Enzymatic activity tests revealed that 50 % of the enzyme activity is preserved. Continuous enzymatic reactions, by the permeation of β-d -glucose through the GOD@ZIF-8 membranes, showed a 50 % increased activity compared to batch experiments, emphasizing the importance of the convective transport of educts and products to and from the enzymatic active centers. 相似文献
18.
Dr. Jun Wang Jaeyoung Heo Dr. Changqiang Chen Dr. Andrew J. Wilson Prof. Prashant K. Jain 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(42):18588-18592
We study how visible light influences the activity of an electrocatalyst composed of Au and Pt nanoparticles. The bimetallic composition imparts a dual functionality: the Pt component catalyzes the electrochemical oxidation of ammonia to liberate hydrogen and the Au component absorbs visible light by the excitation of localized surface plasmon resonances. Under visible-light excitation, this catalyst exhibits enhanced electrochemical ammonia oxidation kinetics, outperforming previously reported electrochemical schemes. We trace the enhancement to a photochemical potential resulting from electron–hole carriers generated in the electrocatalyst by plasmonic excitation. The photopotential responsible for enhanced kinetics scales linearly with the light intensity—a general design principle for eliciting superlative photoelectrochemical performance from catalysts comprised of plasmonic metals or hybrids. We also determine a photochemical conversion coefficient. 相似文献
19.
Felix Unglaube Paul Hünemörder Xuewen Guo Zixu Chen Dengxu Wang Esteban Mejía 《Helvetica chimica acta》2020,103(12):e2000184
The redox activity of molecular phenazine catalysts has been previously exploited for aerobic oxidative amine homo- and cross-coupling reactions. In this contribution, we have extended the reaction scope of this novel type of organocatalyst and used them in the cross-dehydrogenative aza-Henry coupling of isoquinolines with nitromethane under aerobic conditions. Additionally, we have designed and prepared a novel porous organic polymer by cross-linking of tetrakis(4-bromophenyl)silane and dihydrophenazine through Pd-catalyzed Buchwald-Hartwig cross-coupling. This new type of heterogeneous catalyst, apart from being robust and easily reusable, also showed outstanding catalytic activities and improved selectivity compared to its molecular counterpart. A plausible reaction mechanism was proposed based on spectroscopic and kinetic measurements. 相似文献
20.