全文获取类型
收费全文 | 2652篇 |
免费 | 217篇 |
国内免费 | 491篇 |
学科分类
数理化 | 3360篇 |
出版年
2024年 | 6篇 |
2023年 | 110篇 |
2022年 | 69篇 |
2021年 | 98篇 |
2020年 | 102篇 |
2019年 | 65篇 |
2018年 | 76篇 |
2017年 | 91篇 |
2016年 | 124篇 |
2015年 | 118篇 |
2014年 | 167篇 |
2013年 | 181篇 |
2012年 | 146篇 |
2011年 | 160篇 |
2010年 | 125篇 |
2009年 | 177篇 |
2008年 | 157篇 |
2007年 | 167篇 |
2006年 | 160篇 |
2005年 | 179篇 |
2004年 | 127篇 |
2003年 | 110篇 |
2002年 | 71篇 |
2001年 | 56篇 |
2000年 | 73篇 |
1999年 | 61篇 |
1998年 | 45篇 |
1997年 | 50篇 |
1996年 | 39篇 |
1995年 | 33篇 |
1994年 | 48篇 |
1993年 | 26篇 |
1992年 | 28篇 |
1991年 | 20篇 |
1990年 | 18篇 |
1989年 | 12篇 |
1988年 | 15篇 |
1987年 | 12篇 |
1986年 | 2篇 |
1985年 | 9篇 |
1984年 | 4篇 |
1983年 | 5篇 |
1982年 | 4篇 |
1981年 | 7篇 |
1979年 | 6篇 |
1978年 | 1篇 |
排序方式: 共有3360条查询结果,搜索用时 515 毫秒
101.
102.
负载型纳米TiO2复合载体及其CoMo催化剂的酸性及孔特性的研究 总被引:3,自引:0,他引:3
总结了复载不同纳米尺度的复合载体及其CoMo催化剂的表面酸性及孔结构特性的表征结果。结果表明,负载型纳米TiO2与基载体γ-Al2O3存在着相互作用。当负载比较少量的纳米TiO2时,复合载体的总酸量随着TiO2含量的增加而增加,超过γ-Al2O3的酸量,但当 TiO2的含量比较高时复合载体的酸量又降低,纳米TiO2优先负载在γ-Al2O3的强酸中心位;负载了CoMo活性组分后酸量增加。不同粒径的纳米TiO2对复合载体和催化剂的酸分布没有明显影响,但对总酸量有影响。对不同尺度TiO2,随着TiO2负载量的增加以及负载金属活性组分的增加,表面积、孔容和最可几孔径均有不同程度的减少。 相似文献
103.
Three different methods for the preparation and modification of conducting polymer/noble metal catalyst systems consisting of polypyrrole (PPy) and platinum (Pt) are described for the anodic oxidation of methanol. The first method consists of the electrochemical deposition of a thin PPy film on glassy carbon substrate, which is modified with Pt either by electroreduction of hexachloroplatinate, codeposition from a nanodispersed Pt solution, or incorporation of tetrachloroplatinate as counterion followed by cathodic reduction. A second method is based on the preparation of nanoscale PPy(PSS) particles by chemical polymerization with polystyrenesulfonate PSS– as the counterion. This material is a favorable catalyst support for nanodispersed Pt due to its mixed electronic and cationic conductivity. To study the electrochemical properties, the particulate system PPy(PSS)/Pt is fixed in a carbon fiber electrode. A third method was developed which brings the polypyrrole in close contact to a proton exchanger membrane (Nafion) using a special chemical deposition procedure. This method is useful for preparing a membrane electrode assembly (MEA) consisting of Nafion/PPy/Pt. The structural, morphological, and electrocatalytic properties for methanol oxidation were studied depending on the preparation method applied using surface analytical techniques (TEM, SEM, and EDX) and electrochemical measurements (cyclic voltammetry and transient techniques). 相似文献
104.
A series of 2,6-bis(imino)pyridyl iron(II) and cobalt(II) complexes [2,6-(ArNCMe)2C5H3N]MCl2 (Ar = 2,6-i-Pr2C6H3, M = Fe: 3a, M = Co: 4a; Ar = 2,4,6-i-Pr3C6H2, M = Fe: 3b, M = Co: 4b; Ar = 2,6-i-Pr2-4-BrC6H2, M = Fe: 3c, M = Co: 4c; Ar = 2,4-i-Pr2-6-BrC6H2, M = Fe: 3d, M = Co: 4d) has been synthesized, characterized, and investigated as precatalysts for the polymerization of ethylene in the presence of modified methylaluminoxane (MMAO). The substituents of pyridinebisimine ligands and their positions located significantly influence catalyst activity and polymer property. It is found that the catalytic activities of the iron complexes/MMAO systems are mainly dominated by electronical effect, while those of the cobalt complexes/MMAO systems are primarily controlled by hindering effect. 相似文献
105.
The reaction of trimethylbenzene (TMB) over alumina-pillared montmorillonite (Al-PM) had been investigated in a fixed-bed flow reactor at 300 °C and atmospheric pressure. Al-PM calcined in the range 300-500 °C exhibited decreased layer distance, surface area and acid amount. The strong acid sites of Al-PM calcined at 500 °C were greatly diminished according to measurements of ammonia temperature-programmed desorption. Under our conditions the reaction proceeded mainly via isomerization and disproportionation with little dealkylation. The conversion of reactant decreased in the order 1,2,3-TMB ≥ 1,2,4-TMB > 1,3,5-TMB and the selectivity of isomerization in the order 1,2,3-TMB > 1,3,5-TMB > 1,2,4-TMB, corresponding to the order of diminishing thermal instability. Both the catalytic activity and the selectivity ratio of disproportionation to isomerization decreased with increased calcined temperature and time-on-stream. o-Xylene content in the total xylene produced from 1,2,4-TMB or 1,2,3-TMB greatly exceeded the composition at thermodynamic equilibrium. These results arc consistent with the decrease of both the strong acid sites and the pore size of Al-PM which exhibits the restricted transition state selectivity. 相似文献
106.
Poly(ethylene glycol) (PEG)-supported dendrimers have been synthesized using 2.4,6-trichloro-1,3,5-triazine (TCT) as dendrons and tris(hydroxymethyl)aminomethane as tinkers with high loading capacity, excellent solubility and thermal stability by divergent method. The new synthesized PEG-supported G2.0 dendrimer has 10 times as large functional group loading capacity as commercial PEG3400 with overall yield 44.0%. 相似文献
107.
近年来有不少报道从事于生理活性Drimane类倍半萜的合成,较多采用了分子间Diels-Alder反应来建立Drimane的骨架。本文首次采用内分子Diels-Alder反应作为关键反应合成了Drimane类化合物。同时还在引入了手性诱导基团后,首次完成了从无手性的原料化合物β-紫罗兰酮至光学活性(-)-drimenin1的不对称合成。 相似文献
108.
Ezequiel?P.?M.?LeivaEmail author C.?G.?Sánchez 《Journal of Solid State Electrochemistry》2003,7(9):588-592
In the present work, an important point concerning the NEMCA effect is addressed. We analyse the reasons why the changes in the work function of the gas exposed catalyst-electrode surface are one to one related to the changes in the catalyst working electrode potential E with respect to a reference electrode. It is concluded that this is due to the unique properties of the catalyst/solid electrolyte interface: the structure of the double layer in this region is very different from that in liquid electrolytes, being the potential difference at this interface mainly determined by the specific adsorption of the mobile species in the solid electrolyte.
相似文献
Ezequiel P. M. LeivaEmail: |
109.
110.
应用高分子铂络合物催化合成硅烷偶联剂 总被引:1,自引:0,他引:1
以二氧化硅为载体的侧链上含有配位基团和-COOH的聚硅氧烷(1-5)分别与氯铂酸反应制备了五种聚硅氧烷-铂络合物(“St-Pt-l”—“St-Pt-5”).这些高分子铂络合物,用于催化环氧丙基烯丙基醚与三甲及基氢硅烷反应具有很高的催化活性,在温和的条件下(80℃,30min),反应以72—98%的产率生成了硅烷偶联剂γ-(2,3-环氧丙氧基)丙基三甲氧基硅烷.通过对含,配位基的高分子铂络合物“Si-Pt-1”的稳定性研究,发现它可以重复使用多次而不降低其催化活性. 相似文献