全文获取类型
收费全文 | 1475篇 |
免费 | 97篇 |
国内免费 | 217篇 |
专业分类
化学 | 1163篇 |
晶体学 | 20篇 |
力学 | 4篇 |
综合类 | 18篇 |
物理学 | 85篇 |
综合类 | 499篇 |
出版年
2024年 | 5篇 |
2023年 | 10篇 |
2022年 | 42篇 |
2021年 | 45篇 |
2020年 | 48篇 |
2019年 | 41篇 |
2018年 | 34篇 |
2017年 | 45篇 |
2016年 | 56篇 |
2015年 | 56篇 |
2014年 | 42篇 |
2013年 | 136篇 |
2012年 | 99篇 |
2011年 | 69篇 |
2010年 | 52篇 |
2009年 | 78篇 |
2008年 | 71篇 |
2007年 | 92篇 |
2006年 | 80篇 |
2005年 | 84篇 |
2004年 | 74篇 |
2003年 | 56篇 |
2002年 | 59篇 |
2001年 | 49篇 |
2000年 | 46篇 |
1999年 | 47篇 |
1998年 | 53篇 |
1997年 | 32篇 |
1996年 | 31篇 |
1995年 | 31篇 |
1994年 | 22篇 |
1993年 | 21篇 |
1992年 | 19篇 |
1991年 | 13篇 |
1990年 | 5篇 |
1989年 | 11篇 |
1988年 | 6篇 |
1987年 | 6篇 |
1986年 | 5篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1982年 | 5篇 |
1980年 | 2篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1973年 | 1篇 |
1972年 | 1篇 |
排序方式: 共有1789条查询结果,搜索用时 15 毫秒
31.
The electrochemical and in-situ surface-enhanced Raman spectroscopy (SERS) techniques were used to investigate the electrooxidation behavior of methanol in acidic, neutral and alkaline media at a Pt-Ru nanoparticle modified glassy carbon (Pt-Ru/GC) electrode. The results showed that methanol could be dissociated spontaneously at the Pt-Ru/GC electrode to produce a strongly adsorbed intermediate, CO. It was found that CO could be oxidized more easily in the alkaline medium than in the acidic and neutral media. The peak potential of methanol oxidation was shifted from 0.663 and 0.708 V in the acidic and neutral media to -0.030 V in the alkaline medium, which is due to that the adsorption strength of CO on the Pt surface in the alkaline medium is weaker than that in the acidic and neutral media. The final product of the methanol oxidation is CO2. However, in the alkaline medium, CO2 produced would form CO3^2- and HCO3^- resulting in the decrease in the alkaline concentration and then in the decrease in the performance of DMFC. Therefore, the performance of the alkaline DMFC is not Stable. 相似文献
32.
A. El Sayed S. S. Abd El Rehim H. Mansour 《Monatshefte für Chemie / Chemical Monthly》1991,122(12):1019-1027
Summary The electrochemical behaviour of pure indium in KOH solutions (1–4M) was studied at different temperatures (25–70°C) by potentiostatic techniques. Two anodic peaks corresponding to the formation of In(OH)3 and In2O3 were observed. The heights of the two peaks increased with the increase of alkali concentration. An increase of temperature increased the peak currents and shifted their corresponding potentials to more negative values. The variation of the peak currents and peak potentials with scan rate suggested that the anodic dissolution of indium was a diffusion controlled process. In cyclic voltammetry, the reverse scan consistently showed one peak which was attributed to the reduction of anodic oxidation products into indium. X-ray diffraction analysis confirmed the presence of In(OH)3 at the first anodic peak, In(OH)3 and In2O3 at the second anodic peak and In2O3 in the permanent passive region.
Zum elektrochemischen Verhalten einer Indium-Elektrode in konzentrierter Kalilauge bei verschiedenen Temperaturen
Zusammenfassung Es wurde das Verhalten von reinem Indium in 1 – 4M KOH-Lösungen bei Temperaturen zwischen 25 und 70°C mittels potentiostatischer Methoden untersucht. Zwei anodische Peaks, entsprechend der Bildung von In(OH)3 und In2O3, traten auf. Die Höhe der beiden Peaks wurde mit zunehmender Alkalikonzentration gesteigert. Eine Temperaturerhöhung verstärkte die Peakströme und verschob die entsprechenden Potentiale zu negativeren Werten. Die Abhängigkeit der Peakströme und Peakpotentiale von der Scangeschwindigkeit legte den Schluß nahe, daß die anodische Lösung von Indium in einem diffusionskontrollierten Prozeß stattfindet. Bei der cyclischen Voltammetrie zeigte der reverse Scan einheitlich einen Peak, der der Reduktion der anodischen Oxidationsprodukte zu Indium zugeschrieben wurde. Röntgendiffraktionsanalyse bestätigte die Präsenz von In(OH)3 beim ersten anodischen Peak, In(OH)3 beim zweiten Peak und In2O3 im permanent passiven Bereich.相似文献
33.
The purpose of this research was to select an activated carbon and alkaline solution blend that generated the best H2S adsorption on alkaline-activated carbon. RB2 (activated carbon) impregnated with NaOH solution was shown to have the optimum H2S removal efficiency. The optimum NaOH concentration was 50 mg per gram of carbon. H2S adsorption via RB2-NaOH50 was five times that of a corresponding fresh-activated carbon. The adsorption equivalent of H2S is nearly 1 (mol-H2S/mol-AOH), therefore, H2S + AOH AHS + H2O was the major reaction. The H2S adsorption isotherm corresponded to the Freundlich isotherm. 相似文献
34.
采用循环伏安法、旋转金盘电极和库仑电解等方法研究了金在酸性硫脲(TU)溶液中的阳极溶解过程。提出了金的阳极溶解机构。认为表面的Au(TU)_(ads)~ 的“化学溶解”步骤是过程的控制步骤。由此解释了旋转金盘电极的极化曲线出现电流峰以及金的溶解速度出现极大的原因。 相似文献
35.
36.
37.
Fatehy M. Abdel‐Haleem Azza Salah Mahmoud S. Rizk Hussein Moustafa Mikhael Bechelany Ahmed Barhoum 《Electroanalysis》2019,31(4):778-789
Thiourea derivative‐based carbon paste electrode (TUD1‐CPE) was constructed as a potentiometric sensor for the determination of salicylate anion in pharmaceutical formulations, Aspocid® and Aspirin®. The optimized CPE contained 45.5 % graphite, 0.5 % reduced graphene oxide (rGO), 46.0 % nitrophenyl octyl ether (NPOE) plasticizer, 5.0 % TUD1 ionophore, and 3.0 % tridodecylmethyl ammonium chloride as additive. The incorporation of NPOE of high dielectric constant, and rGO in electrode caused better performance of the sensor; Nernstian response of 59.0 mV decade?1 in the concentration range of 10?1–10?5 mole L?1, a detection limit of 1×10?5 mole L?1 in a very short response time of 6 seconds. The prepared sensor showed high selectivity against similar anions (i. e. , benzoate, I?, SCN?). Selectivity was confirmed by calculating the formation constant (Kβ) using sandwich membrane method, where Kβ for TUD1‐salicylate is 100.43. Theoretical calculations at DFT‐B3LY/6‐31G** level of theory were performed to find interaction mechanism, Energies of HOMO and LUMO orbitals, non‐linear optical (NLO) properties (the electronic dipole moment (μ), first‐order hyperpolarizability (β), the hyper‐Rayleigh scattering (βHRS) and the depolarization ratio (DR)), and other global properties; these calculations showed lower values of β and DR, higher value of βHRS, and the shortest lengths of the four N?H bonds between TUD1 and salicylate which confirm their strong complexation and salicylate‐selectivity. Also, all the studied anion‐TUD1 exhibited relatively high NLO properties, and these results were considered as a preliminary study for investigating new types of NLO bearing materials. The sensors were applied successfully for the determination of salicylate anion in Aspocid® and Aspirin®. 相似文献
38.
Custelcean R Gorbunova MG Bonnesen PV 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(5):1459-1466
Hydrogen bonding in crystalline N,N'-dialkylthioureas was examined with the help of single-crystal X-ray diffraction, DFT calculations, and Cambridge Structural Database (CSD) analysis. A CSD survey indicated that unlike the related urea derivatives, which persistently self-assemble into one-dimensional hydrogen-bonded chains, the analogous thioureas can form two different hydrogen-bonding motifs in the solid state: chains, structurally similar with those found in ureas, and dimers, that further associate into hydrogen-bonded layers. The formation of one motif or another can be manipulated by the bulkiness of the organic substituents on the thiourea group, which provides a clear example of steric control over the hydrogen bonding arrangement in crystalline organic solids. 相似文献
39.
40.
G. D. Kolomnikova T. O. Krylova I. V. Chernoglazova P. V. Petrovskii Yu. G. Gololobov 《Russian Chemical Bulletin》1993,42(7):1188-1190
In the presence of trifluoroacetic acid, ethyl 2-cyanoacrylate readily reacts with nucleophilic reagents, such as 2-chloro-1,3,2-benzodioxaphosphole, (EtO)3P, (EtO)2PCl, Ph2PCl, Ph3P, and thiourea. In these reactions the acid proton enters position 2 of the cyanoacrylate, whereas the nucleophilic component enters position 3, in accordance with the electron density distribution in the acrylate. In the absence of trifluoroacetic acid the above reagents, except 2-chloro-1,3,2-benzodioxaphosphole, cause ethyl 2-cyanoacrylate polymerization. The interaction of ethyl 2-cyanoacrylate with 2-chloro-1,3,2-benzodioxaphosphole and trifluoroacetic acid is the first example of a 2-cyanoacrylate taking part in the acid-initiated electrophilic conjugate addition of a weak nucleophile.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1245–1247, July, 1993. 相似文献