全文获取类型
收费全文 | 33887篇 |
免费 | 4969篇 |
国内免费 | 5289篇 |
专业分类
化学 | 17531篇 |
晶体学 | 500篇 |
力学 | 1122篇 |
综合类 | 410篇 |
数学 | 2847篇 |
物理学 | 8373篇 |
无线电 | 13362篇 |
出版年
2024年 | 134篇 |
2023年 | 479篇 |
2022年 | 867篇 |
2021年 | 1015篇 |
2020年 | 939篇 |
2019年 | 1000篇 |
2018年 | 945篇 |
2017年 | 963篇 |
2016年 | 1231篇 |
2015年 | 1493篇 |
2014年 | 1836篇 |
2013年 | 2395篇 |
2012年 | 2582篇 |
2011年 | 2722篇 |
2010年 | 2307篇 |
2009年 | 2322篇 |
2008年 | 2647篇 |
2007年 | 2514篇 |
2006年 | 2263篇 |
2005年 | 2055篇 |
2004年 | 1728篇 |
2003年 | 1439篇 |
2002年 | 1585篇 |
2001年 | 1414篇 |
2000年 | 1095篇 |
1999年 | 742篇 |
1998年 | 457篇 |
1997年 | 441篇 |
1996年 | 393篇 |
1995年 | 340篇 |
1994年 | 277篇 |
1993年 | 280篇 |
1992年 | 236篇 |
1991年 | 181篇 |
1990年 | 152篇 |
1989年 | 145篇 |
1988年 | 94篇 |
1987年 | 83篇 |
1986年 | 59篇 |
1985年 | 59篇 |
1984年 | 44篇 |
1983年 | 34篇 |
1982年 | 22篇 |
1981年 | 33篇 |
1980年 | 16篇 |
1978年 | 15篇 |
1977年 | 9篇 |
1976年 | 11篇 |
1974年 | 8篇 |
1973年 | 7篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Syndiotactic specific polymerization of styrene has been investigated by ~(13)C NMR analysis and isotopic laelling methods. The value of the activation energy involved in the steric control has been determined. Some information of the number of the active sites and on the life of the catalysts is reported. 相似文献
992.
合成了硅胶负载的聚(4-乙烯吡啶)或聚(2-乙烯吡啶)-聚(苯乙烯-顺丁烯二酸)-钯催化剂(P4VP-PSM-Pd/SiO2和P2VP-PSM-Pd/SiO2),研究了合成条件、组成等对其催化性能的影响及对丙烯酸甲酯的催化加氢性能。发现,同时含两种高分子的催化剂比只含一种高分子的催化剂具有较高的催化活性,催化剂在常温常压下对丙烯酸甲酯的氢化反应具有很高的催化活性和选择性,且能重复使用,表现出良好的稳定性。同时还研究了其它因素对催化剂性能的影响。 相似文献
993.
采用水热法合成了一种新的三维配位聚合物[Zn6(bta)4(2,2′-bipy)3](H3bta=1,3,5-苯三乙酸;2,2′-bipy=2,2′-二联吡啶),并通过X射线单晶结构分析、红外光谱、元素分析和热重分析对该配合物进行了表征.结构分析数据表明,该配合物属单斜晶系,Cc空间群,晶胞参数a=1·7714(4)nm,b=2·4391(5)nm,c=1·7120(3)nm,β=104·39(3)°,Z=4,V=7·165(2)nm3,Dc=1·722g/cm3,μ=2·065mm-1,F(000)=3768,R1=0·0645,wR2=0·1424.荧光光谱结果表明,配合物具有良好的荧光性质. 相似文献
994.
Quasi-solid-state electrolytes were fabricated with mesoporous silica SBA-15 as a framework material. Ionic conductivity measurements revealed that SBA-15 can enhance the conductivity of the quasi-solid-state electrolyte. The diffusion coefficients of polyiodide ions such as Ⅰ3ˉ and Ⅰ5ˉ which were confirmed by Raman spectroscopic measurement, were about twice larger than that of I-. The optimized photoenergy conversion efficiency of dye-sensitized solar cells (DSSC) with the quasi-solid-state electrolyte was 4.3% under AM 1.5 irradiation at 75 mW·cm^-2 light intensity. 相似文献
995.
HongBingJI DuGuiHE JunSONG YuQIAN 《中国化学快报》2004,15(10):1241-1244
Clean liquid oxidation of aldehydes can be accomplished using solid catalyst in the presence of molecular oxygen at room temperature, which is a valuable alternative to traditional counterparts. 相似文献
996.
997.
人参挥发油的提取和分析 总被引:7,自引:0,他引:7
应用GC-MS-DS联机分析人参挥发油是当前较好的方法,但人参挥发油的提取方法和GC-MS条件的选择明显影响人参挥发油这一复杂天然混合物的分离和鉴定。本工作严格控制提取条件,提高了挥发油收率,达0.95%;选择最佳GC-MS条件,鉴定出76种化合物,该法稳定重现性好。 相似文献
998.
With the rapid development of human society, clean energy forms are imperative to sustain the normal operations of various mechanical and electrical facilities under a cozy environment. Hydrogen is considered among the most promising clean energy sources for the future. Recently, electrochemical water splitting has been considered as one of the most efficient approaches to harvest hydrogen energy, which generates only non-pollutant water on combustion. However, the sluggish anodic oxygen evolution reaction significantly restricts the efficiency of water splitting and requires a relatively high cell voltage to drive the electrolysis. Therefore, seeking a thermodynamically favorable anodic reaction to replace the sluggish oxygen evolution reaction by utilizing highly active bifunctional electrocatalysts for the anodic reaction and hydrogen evolution are crucial for achieving energy-efficient hydrogen production for industrial applications. Nevertheless, it is known that the oxygen evolution reaction can be replaced with other useful and thermodynamically favorable reactions to reduce the electrolysis voltage for realizing energy-efficient hydrogen production. Therefore, in this study, we present a bifunctional nickel nanoparticle-embedded carbon (Ni@C) prism-like microrod electrocatalyst synthesized via a two-step method involving the synthesis of a precursor metal-organic framework-74 and subsequent carbonization treatment for methanol oxidation and hydrogen evolution. The interfacial structure consisting of a nickel and carbon skeleton was realized via in situ carbonization. However, the dispersed nickel nanoparticles do not easily aggregate owing to the partition by the surrounding carbon as it would sufficiently expose the active Ni sites to the electrolytes, ensuring fast charge transfer between the catalyst and electrolytes by accelerating the electrochemical kinetics. In the anodic methanol oxidation, the products were detected as carbon dioxide and formate with faradaic efficiencies of 36.2% and 62.5%, respectively, at an applied potential of 1.55 V. Meanwhile, the Ni@C microrod catalyst demonstrated high activity and durability (2.7% current decay after 12 h of continuous operation) toward methanol oxidation, which demonstrates that methanol oxidation precedes oxidation under voltage forces. Notably, the bifunctional catalyst not only exhibits excellent performance toward methanol oxidation but also yields a low overpotential of 155 mV to drive 10 mA∙cm−2 toward hydrogen evolution in 1.0 mol∙L−1 KOH aqueous solution with 0.5 mol∙L−1 methanol at room temperature, which guarantees the hydrogen production efficiency. More importantly, the constructed two-electrode electrolyzer produced a current density of 10 mA∙cm−2 at a low cell voltage of 1.6 V, which decreased by 240 mV after replacing the oxygen evolution reaction with methanol oxidation. 相似文献
999.
Jayeon Hong Sangsub Kim Gyurim Park Yongmoon Lee Hyungchae Kim Sungjin Kim Tae-Woo Lee Changsoon Kim Youngmin You 《Chemical science》2021,12(25):8668
Polymer electroluminescence devices producing circularly polarized luminescence (CP PLEDs) have valuable photonic applications. The fabrication of a CP PLED requires a polymer host that provides the appropriate chiral environment around the emitting dopant. However, chemical strategies for the design of chiral polymer hosts remain underdeveloped. We have developed new polymer hosts for CP PLED applications. These polymers were prepared through a free-radical polymerization of 3-vinylcarbazole with a chiral N-alkyl unit. This chiral unit forces the carbazole repeat units to form mutually helical half-sandwich conformers with preferred (P)-helical sense along the polymer main chain. Electronic circular dichroism measurements demonstrate the occurrence of chirality transfer from chiral monomers to achiral monomers during chain growth. The (P)-helical-sense-enriched polymer interacts diastereoselectively with an enantiomeric pair of new phosphorescent (R)- and (S)-dopants. The magnitude of the Kuhn dissymmetry factor (gabs) for the (P)-helically-enriched polymer film doped with the (R)-dopant was found to be one order of magnitude higher than that of the film doped with the (S)-dopant. Photoluminescence dissymmetry factors (gPL) of the order of 10−3 were recorded for the doped films, but the magnitude of diastereomeric enhancement decreased to that of gabs. The chiral polymer host permits faster energy transfer to the phosphorescent dopants than the achiral polymer host. Our photophysical and morphological investigations indicate that the acceleration in the chiral polymer host is due to its longer Förster radius and improved compatibility with the dopants. Finally, multilayer CP PLEDs were fabricated and evaluated. Devices based on the chiral polymer host with the (R)- and (S)-dopants exhibit electroluminescence dissymmetry factors (gEL) of 1.09 × 10−4 and −1.02 × 10−4 at a wavelength of 540 nm, respectively. Although challenges remain in the development of polymer hosts for CP PLEDs, our research demonstrates that chiroptical performances can be amplified by using chiral polymer hosts.Polymer electroluminescence devices producing circularly polarized luminescence (CP PLEDs) have valuable photonic applications. 相似文献
1000.
KANG Yong-Feng LIU Lei YAN Wen-Jin XU Zhao-Qing ZHOU Yi-Feng HAN Zhi-Jian NI Ming DA Chao-Shan WANG Rui 《有机化学》2004,24(Z1):163
Development of new or improved methods for the asymmetric preparation of chiral propargylic alcohols has gained considerable significance during the past years because they are useful building blocks for the synthesis of many biologically active compounds and natural products.[1] A series of chiral tridentate ligands were conveniently synthesized from amino acids with good yields (Scheme 1).[2] A preliminary study of the enantioselective alkynylation of benzaldehyde catalyzed by this chiral tridentate ligand was carried out and up to 83% ee of chiral propargyl alcohols was obtained (Table 1 ). A further investigation of the tridentate ligand is currently underway. 相似文献