全文获取类型
收费全文 | 3451篇 |
免费 | 280篇 |
国内免费 | 772篇 |
专业分类
化学 | 1752篇 |
晶体学 | 7篇 |
力学 | 283篇 |
综合类 | 14篇 |
数学 | 123篇 |
物理学 | 194篇 |
综合类 | 2130篇 |
出版年
2024年 | 17篇 |
2023年 | 44篇 |
2022年 | 48篇 |
2021年 | 80篇 |
2020年 | 96篇 |
2019年 | 84篇 |
2018年 | 90篇 |
2017年 | 100篇 |
2016年 | 130篇 |
2015年 | 131篇 |
2014年 | 165篇 |
2013年 | 205篇 |
2012年 | 232篇 |
2011年 | 267篇 |
2010年 | 210篇 |
2009年 | 213篇 |
2008年 | 241篇 |
2007年 | 284篇 |
2006年 | 241篇 |
2005年 | 241篇 |
2004年 | 204篇 |
2003年 | 201篇 |
2002年 | 151篇 |
2001年 | 149篇 |
2000年 | 118篇 |
1999年 | 102篇 |
1998年 | 63篇 |
1997年 | 72篇 |
1996年 | 52篇 |
1995年 | 60篇 |
1994年 | 39篇 |
1993年 | 39篇 |
1992年 | 26篇 |
1991年 | 32篇 |
1990年 | 17篇 |
1989年 | 24篇 |
1988年 | 13篇 |
1987年 | 7篇 |
1986年 | 3篇 |
1984年 | 1篇 |
1983年 | 2篇 |
1982年 | 1篇 |
1981年 | 2篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1977年 | 1篇 |
1973年 | 1篇 |
1955年 | 2篇 |
排序方式: 共有4503条查询结果,搜索用时 31 毫秒
71.
As supported PtxNi1–x catalysts are used for hydrogenation reactions, it seemed necessary to assess the surface composition of the reduced samples. To approach the usual reduction conditions we applied in situ reduction in a reaction chamber (1 mbar H2 up to 500 °C) placed in ultra high vacuum recipient (UHV: 10–9 to 2.10–10mbar). All ion scattering spectroscopy measurements were performed in UHV. Charging of the samples was avoided by electron bombardment (5 eV). The variation of the surface composition was determined after subsequent sputtering, thermal treatment at 500 °C and during oxygen adsorption. A comparison with previous results of surface compositions of binary alloys (polycrystalline foils [1, 2] and single crystals PtxNi1–x [3]) is given.Dedicated to Professor Dr. rer. nat. Dr. h. c. Hubertus Nickel on the occasion of his 65th birthday 相似文献
72.
Preparation of Nano-Sized γ-Al2O3 Supported Iron Catalyst for Fischer-Tropsch Synthesis by Solvated Metal Atom Impregnation Methods
下载免费PDF全文
![点击此处可从《天然气化学杂志》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Two types of small iron clusters supported on γ-Al2O3-RT(dehydroxylated at room temperature) and γ-Al2O3-800 (dehydroxylated at 800 ℃) were prepared by solvated metal atom impregnation (SMAI) techniques. The iron atom precursor complex, bis(toluene)iron(0) formed in the metal atom reactor, was impregnated into γ-Al2O3 having different concentrations of surface hydroxyl groups to study the effect of surface hydroxylation on the crucial stage of iron cluster formation. Catalysts prepared in this way were characterized by TEM, M(o)ssbauer, and chemisorption measurements, and the results show that higher concentration of surface hydroxyl groups of γ-Al2O3-RT favors the formation of more positively charged supported iron cluster Fen/γ-Al2O3-RT, and the lower concentration of surface hydroxyl groups of γ-Al2O3-800 favors the formation of basically neutral supported iron cluster Fen/γ-Al2O3-800. The measured results also indicate that the higher concentration of surface hydroxyl groups causes the rapid decomposition of precursor complex, bis(toluene)iron(0), and favors the formation of relatively large iron cluster. Consequently, these two types of catalysts show different catalytic properties in Fischer-Tropsch reaction. The catalytic pattern of Fen/γ-Al2O3-RT in F-T reaction is similar to that of the unreduced α-Fe2O3 and that of Fen/γ-Al2O3-800 is similar to that of the reduced α-Fe2O3. 相似文献
73.
粉末化学镀法制备的NiB/TiO2非晶态合金催化剂对环丁烯砜加氢反应的催化性能 总被引:7,自引:0,他引:7
采用诱导沉积法及粉末化学镀法分别制备了纯态NiB及负载型NiB/TiO2非晶态合金催化剂.用XRD,ICP,SEM,TEM和DSC等手段对催化剂的物性及TiO2载体与NiB非晶态合金之间的相互作用进行了表征,考察了非晶态合金的结构、组成、形貌和热稳定性,并将其用于环丁烯砜加氢反应中.结果表明,相对于NiB而言,NiB/TiO2催化剂具有优良的热稳定性和催化活性,这缘于NiB和TiO2载体之间的相互作用及载体的分散作用. 相似文献
74.
Sébastien L.X. Martina 《Tetrahedron letters》2004,45(16):3279-3282
Novel solid-supported phosphonate reagents have been prepared and evaluated for the synthesis of α,β-unsaturated esters with a preference for the Z-alkene. The optimal reagent was a hybrid of both Still-Gennari and Ando reagents, and showed good to high yields and fair to good Z-selectivity for the conversion of both aliphatic and aromatic aldehydes. 相似文献
75.
Ag/Al2O3选择性催化丙烯还原氮氧化物表面反应机理的原位红外光谱研究 总被引:2,自引:0,他引:2
在富氧条件下Ag/Al2O3对以丙烯为还原剂选择性催化还原NOx的反应有很高的催化活性.本实验成功地利用原位红外光谱分析手段,在真实的催化反应条件下,探讨了丙烯选择性还原NOx的反应机理,证实了催化剂表面反应中间体Al-NCO和Ag-NCO虽在真空中稳定,但在实际反应条件下极为活泼.催化剂表面上R-ONO和R-NO2分解成NCO是整个反应的速度控制步骤.这一结论与在真空系统条件下对其反应机理的研究结果一致,证明了在这一反应体系中两种研究方法的相关性.同时本实验还从反应机理上探讨了催化剂的水蒸气中毒现象.水蒸气的存在阻碍了催化剂表面R-ONO和R-NO2的生成,并进一步阻碍了反应的速度控
制步骤,即R-ONO和R-NO2向Al-NCO和Ag-NCO的转化,但这是一种完全可逆的暂时中毒现象.结合相应的催化剂活性评价结果对表面反应机理进行了讨论. 相似文献
76.
In this paper, zinc tetraaminophthalocyanine (Zn-APc) was immobilized on cellulosic fiber by covalent bond to obtain a novel cellulosic fiber supported metallophthalocyanine, named Zn-TDTAPc-F. At pH 11, upon visible light irradiation for 6 h in the presence of O2, Zn-TDTAPc-F was found to be highly effective for the degradation of phenol in aqueous solution, and the degradation rate of phenol was more than 95%. HPLC was used to confirm formic acid, fumaric acid and maleic acid as its main degradation products. 相似文献
77.
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
78.
非晶态NiP(B)/Al2O3催化一氧化碳,水和氧气合成过氧化氢 总被引:1,自引:0,他引:1
Hydrogenperoxideisagreenoxidantwithgreatpotentialformuchapplication .Thepresentproduc tionofhydrogen peroxiderequiressevereconditionsand generates pollutants .AlternativesynthesesarerequiredandthesynthesisofH2 O2 fromCO ,H2 OandO2 isverypromising .AsshowninEq(1) ,thesynthesisisthermodynamicallyfavored :CO +H2 O +O2 H2 O2 +CO2 (1)ΔG02 98=- 134kJ/mol ThereactionwasfirstreportedbyZudinetal[1]whousedpalladiumtriphenylphosphaneasacatalyst.Bianchietal[2 ] usedabiphasesystemforthesynthe … 相似文献
79.
Novel polymer supported IBX esters and amides were prepared in two steps, which were the coupling of 2-iodobenzoic acid to a hydroxy or amino polystyrene followed by activation of the intermediate product. These polymer supported reagents were tested as oxidants by the conversion of a series of alcohols to the corresponding aldehydes or ketones. We found that the polymer supported IBX amides displayed excellent oxidative activity, in that they oxidized benzyl alcohol to benzaldehyde completely within 1 h at an oxidant to alcohol ratio of 2 to 1. 相似文献
80.