全文获取类型
收费全文 | 10174篇 |
免费 | 449篇 |
国内免费 | 1541篇 |
专业分类
化学 | 11366篇 |
晶体学 | 42篇 |
力学 | 33篇 |
综合类 | 44篇 |
数学 | 11篇 |
物理学 | 668篇 |
出版年
2023年 | 145篇 |
2022年 | 100篇 |
2021年 | 211篇 |
2020年 | 240篇 |
2019年 | 332篇 |
2018年 | 214篇 |
2017年 | 365篇 |
2016年 | 259篇 |
2015年 | 298篇 |
2014年 | 409篇 |
2013年 | 407篇 |
2012年 | 872篇 |
2011年 | 628篇 |
2010年 | 483篇 |
2009年 | 603篇 |
2008年 | 703篇 |
2007年 | 811篇 |
2006年 | 730篇 |
2005年 | 704篇 |
2004年 | 706篇 |
2003年 | 443篇 |
2002年 | 326篇 |
2001年 | 249篇 |
2000年 | 241篇 |
1999年 | 226篇 |
1998年 | 214篇 |
1997年 | 203篇 |
1996年 | 141篇 |
1995年 | 134篇 |
1994年 | 137篇 |
1993年 | 126篇 |
1992年 | 114篇 |
1991年 | 99篇 |
1990年 | 97篇 |
1989年 | 63篇 |
1988年 | 39篇 |
1987年 | 16篇 |
1986年 | 15篇 |
1985年 | 10篇 |
1984年 | 8篇 |
1983年 | 3篇 |
1982年 | 8篇 |
1981年 | 3篇 |
1980年 | 4篇 |
1979年 | 3篇 |
1977年 | 3篇 |
1976年 | 7篇 |
1975年 | 2篇 |
1972年 | 3篇 |
1969年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
1.
《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
2.
3.
提出用溶胶粒子表面修饰方法,结合溶胶凝胶技术制备无机催化膜.该方法的基本原理是利用合适的金属配合物在胶粒表面的吸附作用,经溶胶凝胶过程,将活性组分结合到无机膜中.实验测定结果表明:(NiEDTA)2-,VO-3,MoO2-4,(Pd(NH3)4)2+,PdCl2-4,PtCl2-6和RhCl3-6可用来修饰AlOOH溶胶.以Pd/γAl2O3催化膜的制备为例,经三次溶胶凝胶过程,可制得无裂缺的厚度为9μm的Pd/γAl2O3催化膜,膜材料的平均孔直径为6nm,Pd被均匀地分布在膜的顶层,其平均粒径为23nm. 相似文献
4.
Susana Conde Ceide 《Tetrahedron letters》2006,47(26):4415-4418
We herein report that flash heating microwave irradiation is a helpful tool in the formation of arylpyrimidines from the corresponding halopyrimidines. The palladium-catalyzed cross-coupling reactions of 2,4-di- and 2,4,5-trihalopyrimidines with phenylboronic acid under the above conditions are described. By use of the appropriate catalyst and the adequate halopyrimidine, good regioselectivity can be achieved in the 2-, 4-, or 5-positions of the heterocycle. In addition, we show that this methodology is ameneable for the stepwise preparation of mono-, di-, and triphenylpyrimidines. 相似文献
5.
Shufeng Zuo 《Applied Surface Science》2006,253(5):2508-2514
Al-pillared clays supported rare earths (RE/Al-PILC) are prepared and used as supports of palladium catalysts for deep oxidation of low concentrations of benzene (130-160 ppm). The supports and catalysts are characterized by X-ray powder diffraction (XRD), FT-IR, BET, transmission electron microscopy (TEM) and temperature-programmed reduction (H2-TPR). The results show that Al-pillaring results in a strong increase in the basal spacing (d0 0 1) from about 1.2 to 1.8 nm, and an increase in the BET surface area from 63.6 (±3.2) to 238.8 (±11.9) m2/g. Activity tests of deep oxidation of low concentration benzene show catalysts supported on Al-PILC and RE/Al-PILC are obviously more active than that on raw clay. Pd/6% Ce/Al-PILC, in particular, can catalyze the complete oxidation of low concentration benzene at a temperature as low as about 290 °C. 相似文献
6.
A. V. Semykin I. A. Kazarinov E. A. Khomskaya 《Russian Journal of Electrochemistry》2006,42(6):643-648
The hydrogen ionization process is studied experimentally on an industrial sintered nickel oxide electrode in models of sealed nickel-metal hydride batteries. It is shown that the hydrogen ionization rates that are reached during overcharge by high current densities in conditions of forced gas delivery into the electrode pores (up to 40 mA cm?2) exceed the self-discharge rate of a nickel-hydrogen battery by two orders of magnitude. Up to 70% of hydrogen delivered into the compact assembly block undergoes ionization during forced charge of models of sealed nickel-metal hydride batteries with a closed hydrogen cycle. Two independent methods (potentiostatic and manometric) are used to determine the relationship between rates of hydrogen ionization with the degree of the electrode filling with gas and perform estimation of the process intensity at a unit reaction surface. It is established that, in conditions of forced gas delivery, practically all the hydrogen oxidation current is generated at the surface of the nickel oxide electrode beneath thin films of an electrolyte solution at the rate of 4–5 mA cm?2. It is shown that the hydrogen oxidation rate on a nickel oxide electrode filled in part by gas is independent of the electrode potential, probably because of a tangible contribution made by diffusion limitations to the overall hampering of the process. 相似文献
7.
关新民 《新疆大学学报(理工版)》2002,19(1):95-99
介绍了采用MATLAB V5.2提供的模糊逻辑工具箱来设计研究电孤纺电极调节系统中的模糊--PD控制器,讨论了在SIMULINK环境下模糊-PD控制器的参数自调速原理、结构、建立模糊控制规则库和模糊推论方法,并给出仿真结果与结论。 相似文献
8.
A new electroactive polynuclear inorganic compound of rare earth metal, gadolinium hexacyanoferrate (GdHCF), was prepared and characterized using the techniques of FTIR spectroscopy, thermogravimetric analysis (TG), UV-Vis spectrometry, X-ray photoelectron spectroscopy (XPS), ICP atomic emission spectroscopy, and EDX. The results of ICP atomic emission spectroscopy, EDX, and TGA indicated that the prepared GdHCF sample had a stoichiometry of NaGdFe(CN)6·12H2O (when GdHCF was prepared in NaCl solution). The FTIR spectrum of GdHCF showed that there were two types of water molecules in the structure of GdHCF: one was the interstitial water (5 H2O), which resulted from the association of water due to H-bonding, and the other was water coordinated with Gd (7 H2O). The results obtained using XPS showed that the oxidation state of Fe and Gd in the GdHCF sample was +2 and +3, respectively. GdHCF was immobilized on the surface of spectroscopically pure graphite (SG) electrode forming the GdHCF/SG electrode, and the solid-state electrochemistry of the resultant electrode was studied using cyclic voltammetry. The cyclic voltammetric results indicated that the GdHCF/SG electrode exhibited a pair of well-defined and stable redox peaks with the formal potential of E0′=(197±3) mV. The effects of the concentration of the supporting electrolyte on the electrochemical characteristics of GdHCF were studied, and the results showed that the value of E0′ increased linearly with the activity of the cationic ion of the supporting electrolyte (lgaNa+), with a slope of 54.1 mV, which may become a novel method for determining the activity of Na+ in solution. Further experimental results indicated that GdHCF had electrocatalytic activities toward the oxidation of dopamine (DA) and ascorbic acid (AA), and the electrocatalytic current increased linearly with the concentration of DA (or AA) in the range of 1.0–10.0 mmol·L?1 (for DA) or 0.5–20.0 mmol·L?1 (for AA). 相似文献
9.
Palladium-catalysed three component coupling of an alkenylbromide, isonitrile and an amine or alkoxide/phenoxide affords α,β-unsaturated-amidines and -imidates. 相似文献
10.
Results of two urgent and practically important directions of research on the indirect oxidation of organic compounds by highly reactive intermediates generated electrochemically from oxygen (HO2
–, HO2
·, HO·) are considered and orderly arranged. The studies in question are the indirect synthesis and mineralization of organic toxicants in waste water. 相似文献