全文获取类型
收费全文 | 6177篇 |
免费 | 416篇 |
国内免费 | 1312篇 |
专业分类
化学 | 7329篇 |
晶体学 | 34篇 |
力学 | 32篇 |
综合类 | 42篇 |
数学 | 15篇 |
物理学 | 453篇 |
出版年
2023年 | 67篇 |
2022年 | 85篇 |
2021年 | 189篇 |
2020年 | 173篇 |
2019年 | 182篇 |
2018年 | 131篇 |
2017年 | 173篇 |
2016年 | 208篇 |
2015年 | 209篇 |
2014年 | 239篇 |
2013年 | 277篇 |
2012年 | 668篇 |
2011年 | 314篇 |
2010年 | 292篇 |
2009年 | 367篇 |
2008年 | 422篇 |
2007年 | 499篇 |
2006年 | 460篇 |
2005年 | 419篇 |
2004年 | 420篇 |
2003年 | 307篇 |
2002年 | 227篇 |
2001年 | 174篇 |
2000年 | 158篇 |
1999年 | 147篇 |
1998年 | 133篇 |
1997年 | 148篇 |
1996年 | 96篇 |
1995年 | 111篇 |
1994年 | 107篇 |
1993年 | 109篇 |
1992年 | 93篇 |
1991年 | 86篇 |
1990年 | 85篇 |
1989年 | 48篇 |
1988年 | 30篇 |
1987年 | 10篇 |
1986年 | 12篇 |
1985年 | 7篇 |
1984年 | 7篇 |
1983年 | 2篇 |
1982年 | 7篇 |
1981年 | 3篇 |
1980年 | 1篇 |
1978年 | 1篇 |
1976年 | 1篇 |
1972年 | 1篇 |
排序方式: 共有7905条查询结果,搜索用时 31 毫秒
1.
This review summarizes recent progress in understanding the oxygen reduction and evolution reactions at the lanthanum strontium manganite electrode of a high-temperature solid oxide cell. Information provided here is put into the perspective of the defect chemistry of lanthanum strontium manganite and its impact on the electrode reaction mechanisms itself. After summarizing recent views on the oxygen reduction reaction mechanism, the focus turns to the oxygen evolution reaction, which is significantly less treated in the literature. A combination of the information in the literature on both reactions was the basis for modified reaction mechanism of the oxygen evolution reaction to be proposed under consideration of recent experimental observations and theoretical findings. 相似文献
2.
固体氧化物电解池可高效地电解H2O/CO2制备燃料,越来越受到人们的重视. 本文对近年来在燃料电极(阴极)材料方面的研究进展进行了全面综述,指出各种阴极材料的优缺点及发展趋势,强调亟待解决的关键科学与技术问题. 相似文献
3.
DNA release electrochemically stimulated by applying ?10 mV on the modified electrode was studied. The release process was based on the local (interfacial) pH change produced upon H2O2 reduction electrocatalyzed by the immobilized microperoxidase‐11. SiO2 nanoparticles attached to the electrode surface and functionalized with trigonelline and boronic acid species changed their electrical charge from positive to negative upon the interfacial pH change, thus allowing electrostatic adsorption of negatively charged DNA on the positive interface and then its repulsion/release from the negative interface. The loaded/released DNA molecules were labeled with a fluorescent dye to allow easy detection of the released DNA molecules. The important feature of the developed system is the controlled DNA release upon applying very small electrical potential on the modified electrode. 相似文献
4.
《Comptes Rendus Chimie》2015,18(9):993-1000
The electrochemical oxidation of N-acetyl-p-aminophenol (PAR) was investigated at a Pt electrode with the application of cyclic (CV) and differential pulse (DPV) voltammetry methods. An effect of scan rate, substrate concentration and pH on electrode reactions was determined. The parameters of substrate electro-oxidation, i.e. heterogeneous rate constant, charge transfer coefficient, and diffusion coefficient, were calculated. Our investigation's results prove the exchange of two electrons and one proton in the first step, followed by a chemical reaction. PAR electro-oxidation occurs according to an EC mechanism. 相似文献
5.
Chloride‐Selective Electrodes Based on “Two‐Wall” Aryl‐Extended Calix[4]Pyrroles: Combining Hydrogen Bonds and Anion–π Interactions to Achieve Optimum Performance 下载免费PDF全文
Jad Sabek Dr. Louis Adriaenssens Tomàs Guinovart Dr. Enrique J. Parra Prof. F. Xavier Rius Prof. Pablo Ballester Dr. Pascal Blondeau 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):448-454
The performance of chloride‐selective electrodes based on “two‐wall” aryl‐extended calix[4]pyrroles and multiwall carbon nanotubes is presented. The calix[4]pyrrole receptors bear two phenyl groups at opposite meso‐positions. When the meso‐phenyl groups are decorated with strong electron‐withdrawing substituents, attractive anion–π interactions may exist between the receptor’s aromatic walls and the sandwiched anion. These anion–π interactions are shown to significantly affect the selectivity of the electrodes. Calix[4]pyrrole, bearing a p‐nitro withdrawing group on each of the meso‐phenyl rings, afforded sensors that display anti‐Hofmeister behavior against the lipophilic salicylate and nitrate anions. Based on the experimental data, a series of principles that help in predicting the suitability of synthetic receptors for use as anion‐specific ionophores is discussed. Finally, the sensors deliver excellent results in the direct detection of chloride in bodily fluids. 相似文献
6.
Methylthiouracil‐modified Carbon Paste Electrode as a New Voltammetric Sensor Based on a 1,4‐Michael Addition Reaction for Detection of Dopamine 下载免费PDF全文
M. Arab Chamjangali A. Ahmadi Reskety N. Goudarzi G. Bagherian 《Electroanalysis》2015,27(12):2708-2717
A sensitive dopamine sensor was constructed based on the modified carbon paste electrode with methylthiouracil as a nucleophile in the 1,4‐Michael addition reaction. An ECE mechanism was suggested for dopamine oxidation at the modified electrode. Design of experiments was used in the optimization of variables. Under the optimum conditions, calibration graph was linear in the range of 0.20–15.0 µM with a detection limit of 73 nM. The relative standard deviations (n=5) for 0.50 µM of dopamine was 3.83 %. The selectivity of the sensor was also studied. The developed sensor was applied for analysis of pharmaceutical and biological samples. 相似文献
7.
N‐coordinate Pd2+ complexes [PdL2] (L: N‐N‐quinoline‐8‐yl‐R‐benzenesulfonamides) ( 6–10 ) and [PdL2] complexes assembled on multi‐wall carbon nanotubes (MWCNTs) hybrid nanomaterials were fabricated and characterized by various techniques. The [PdL2] impregnated MWCNTs materials ( 11–15 ) were applied as a counter electrode (CE) catalyst for triiodide to iodide reduction reaction in the dye‐sensitized solar cells (DSSC) and investigated electro‐catalytic activities. The MWCNTs‐supported [PdL2] CEs ( 11–15 ) are exhibits as Pt‐free CE with good power conversion efficiencies (PCEs), and compared to platinum and bare MWCNTs CEs and the PCE of bare MWCNTs was clearly improved by means of [PdL2] complexes ( 6–10 ). The DSSCs based on the hybrid counter electrodes (CEs) ( 11–15 ) and bare MWCNTs are indicated a relative efficiency ( ? rel ) of 64.27%, 54.07%, 53.75%, 51.52% 44.82% and 27.27% concerning a Pt CE control device set at 100%. The report emphasizes that [PdL2] impregnated MWCNTs type counter electrodes (CEs) ( 11–15 ) are promising as effectively catalyst in working device design, particularly taking into account the eco‐friendly approach of the hybrids. 相似文献
8.
Yassine Benmassaoud Khaled Murtada Rachid Salghi Mohammed Zougagh ngel Ríos 《Molecules (Basel, Switzerland)》2021,26(9)
In this study, we combine magnetic solid phase extraction (MSPE), with the screen-printed carbon electrode (SPCE) modified by a molecular imprinted polymer (MIP) for sensitive and selective extraction and electrochemical determination of Rhodamine B in food samples. A magnetic solid phase extraction (MSPE) was carried out using magnetic poly(styrene-co-divinylbenzene) (PS-DVB) and magnetic nanoparticles (MNPs) synthetized on the surface of multiwalled carbon nanotubes (MWCNTs). An MIP was prepared on the surface of MWCNTs in the presence of titanium oxide nanoparticles (TiO2NPs) modifying the SPCE for the rapid electrochemical detection of Rhodamine B. The MIPs synthesis was optimized by varying the activated titanium oxide (TiO2) and multiwalled carbon nanotubes (MWCNTs) amounts. The MSPE and electrochemical detection conditions were optimized as well. The present method exhibited good selectivity, high sensitivity, and good reproducibility towards the determination of Rhodamine B, making it a suitable method for the determination of Rhodamine B in food samples. 相似文献
9.
Organic electrode materials (OEMs) are being investigated as promising candidates for aqueous zinc-ion batteries (AZIBs) owing to their environmental friendliness, cost-effectiveness, and structural diversity, and tunability. Understanding the correlation between structural regulation of OEMs and their electrochemical property in AZIBs is vital to rational design of OEMs. Herein, we first discuss the fundamentals of the energy storage mechanism of OEMs. Then, strategies to improve the electrochemical performance, including the specific capacity, voltage, rate capability, and cycling stability, are elaborated from the perspective of molecular engineering. Finally, we share our views on the remaining challenges and prospects of OEMs in AZIBs. 相似文献
10.
Tahya Bamine Edouard Boivin Christian Masquelier Laurence Croguennec Elodie Salager Dany Carlier 《Magnetic resonance in chemistry : MRC》2020,58(11):1109-1117
7Li, 31P, and 19F solid-state nuclear magnetic resonance (NMR) spectroscopy was used to investigate the local arrangement of oxygen and fluorine in LiVPO4F1-yOy materials, interesting as positive electrode materials for Li-ion batteries. From the evolution of the 1D spectra versus y, 2D 7Li radiofrequency-driven recoupling (RFDR) experiments combined, and a tentative signal assignment based on density functional theory (DFT) calculations, it appears that F and O are not randomly dispersed on the bridging X position between two X–VO4–X octahedra (X = O or F) but tend to segregate at a local scale. Using DFT calculations, we analyzed the impact of the different local environments on the local electronic structure. Depending on the nature of the VO4X2 environments, vanadium ions are either in the +III or in the +IV oxidation state and can exhibit different distributions of their unpaired electron(s) on the d orbitals. Based on those different local electronic structures and on the computed Fermi contact shifts, we discuss the impact on the spin transfer mechanism on adjacent nuclei and propose tentative signal assignments. The O/F clustering tendency is discussed in relation with the formation of short VIVO vanadyl bonds with a very specific electronic structure and possible cooperative effect along the chain. 相似文献