首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   19992篇
  免费   3445篇
  国内免费   3620篇
化学   15788篇
晶体学   374篇
力学   869篇
综合类   266篇
数学   2195篇
物理学   7565篇
  2024年   52篇
  2023年   361篇
  2022年   666篇
  2021年   754篇
  2020年   852篇
  2019年   840篇
  2018年   748篇
  2017年   821篇
  2016年   1033篇
  2015年   1081篇
  2014年   1313篇
  2013年   1672篇
  2012年   2058篇
  2011年   2093篇
  2010年   1571篇
  2009年   1459篇
  2008年   1565篇
  2007年   1398篇
  2006年   1254篇
  2005年   950篇
  2004年   670篇
  2003年   560篇
  2002年   647篇
  2001年   572篇
  2000年   385篇
  1999年   359篇
  1998年   213篇
  1997年   175篇
  1996年   145篇
  1995年   125篇
  1994年   108篇
  1993年   110篇
  1992年   76篇
  1991年   67篇
  1990年   52篇
  1989年   46篇
  1988年   30篇
  1987年   33篇
  1986年   35篇
  1985年   21篇
  1984年   15篇
  1983年   13篇
  1982年   13篇
  1980年   4篇
  1977年   5篇
  1974年   4篇
  1973年   5篇
  1972年   4篇
  1971年   5篇
  1957年   4篇
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
951.
The mechanisms of the thermal degradation of polyhedral oligomeric octaphenylsilsesquioxane (OPS), octa(nitrophenyl)silsesquioxane (ONPS), and octa(aminophenyl)silsesquioxane (OAPS) were investigated. The –NO2 or –NH2 substituents on the phenyl group affected the mechanism of the POSS thermal degradation. The thermal stabilities of OPS, ONPS, and OAPS were characterized by TG and FTIR. Thermal degradation of OPS included mainly the degradation of caged polyhedral oligomeric silsesquioxane structures and phenyl groups. Nitro or amino substituents decreased its thermal stability. The thermal degradation processes of OPS, ONPS, and OAPS differed. Phenyl groups and cyclobutadiene were observed in the OPS degradation products. Oxygen radicals that caused intensive CO2 release between 350 and 450 °C were generated by the degradation of ONPS –NO2. OAPS released mainly aminophenyl groups at 370 °C, whereas a small number of phenyl groups decomposed at 500 °C. The OAPS reactivity could enhance the thermal stability of POSS structure in the polyimide OAPS composites.  相似文献   
952.
Zeolitic imidazolate framework-8 (ZIF-8) is synthesized by typical solvothermal method and subsequently calcined under air and nitrogen atmosphere, respectively. The carbon in the calcined ZIF-8 under nitrogen atmosphere was from the carbonization of the guest molecules, without adding any other carbon sources. The samples are characterized by X-ray diffraction, Fourier transform infrared spectroscopy, and electrochemical analyzer system. When the ZIF-8 is used as electrode materials for a supercapacitor in 6 M KOH electrolyte, it displays a pseudocapacitive behavior. The untreated ZIF-8 and calcined ZIF-8 under air and nitrogen atmosphere electrodes exhibit a specific capacitance of 96, 156, and 185 F g?1, respectively, at a scan rate of 5 mV s?1 and good stability over 1,500 cycles. These results indicate that the ZIF-8 is a promising material for supercapacitors.  相似文献   
953.
Noble metal nanocrystals (NCs) enclosed with high‐index facets hold a high catalytic activity thanks to the high density of low‐coordinated step atoms that they exposed on their surface. Shape‐control synthesis of the metal NCs with high‐index facets presents a big challenge owing to the high surface energy of the NCs, and the shape control for metal Rh is even more difficult because of its extraordinarily high surface energy in comparison with Pt, Pd, and Au. The successful synthesis is presented of tetrahexahedral Rh NCs (THH Rh NCs) enclosed by {830} high‐index facets through the dynamic oxygen adsorption/desorption mediated by square‐wave potential. The results demonstrate that the THH Rh NCs exhibit greatly enhanced catalytic activity over commercial Rh black catalyst for the electrooxidation of ethanol and CO.  相似文献   
954.
Magnolol and honokiol as pharmaceutical ligands have been introduced into terbium complex systems for the first time and two hybrid organic–inorganic materials were successfully prepared. Both of them can sensitize terbium characteristic green emission effectively based on intra-molecular energy transfer channel. Moreover, they selectively recognized Cu2+ and Fe3+ through luminescence quenching effects. The photophysical properties and morphological structures were extensively investigated.  相似文献   
955.
A novel method for the synthesis of 1,4‐diketones from β‐ketosulfones was developed by means of a visible light‐induced C?S bond activation process. Symmetrical and unsymmetrical 1,4‐diketones can be easily prepared in moderate to good yields.  相似文献   
956.
cis‐2,6‐Tetrahydropyran is an important structural skeleton of bioactive natural products. A facile synthesis of cis‐2,6‐disubstituted‐3,6‐dihydropyrans as cis‐2,6‐tetrahydropyran precursors has been achieved in high regio‐ and stereoselectivity with high yields. This reaction involves a palladium‐catalyzed decarboxylative allylation of various 3,4‐dihydro‐2H‐pyran substrates. Extending this reaction to 1,2‐unsaturated carbohydrates allowed the achievement of challenging β‐C‐glycosylation. Based on this methodology, the total syntheses of (±)‐centrolobine and (+)‐decytospolides A and B were achieved in concise steps and overall high yields.  相似文献   
957.
958.
The correspondence between triplet location effect and host‐localized triplet–triplet annihilation and triplet–polaron quenching effects was performed on the basis of a series of naphthyldiphenylamine (DPNA)‐modified phosphine oxide hosts. The number and ratio of DPNA and diphenylphosphine oxide was adjusted to afford symmetrical and unsymmetrical molecular structures and different electronic environments. As designed, the first triplet (T1) states were successfully localized on the specific DPNA chromophores. Owing to the meso‐ and multi‐insulating linkages, identical optical properties and comparable electrical performance was observed, including the same first singlet (S1) and T1 energy levels to support the similar singlet and triplet energy transfer and the close frontier molecular orbital energy levels. This established the basis of rational investigation on T1 location effect without interference from other optoelectronic factors.  相似文献   
959.
The activation of C?H bonds in alkanes is currently a hot research topic in chemistry. The atomic oxygen radical anion (O?.) is an important species in C?H activation. The mechanistic details of C?H activation by O?. radicals can be well understood by studying the reactions between O?. containing transition metal oxide clusters and alkanes. Here the reactivity of scandium oxide cluster anions toward n‐butane was studied by using a high‐resolution time‐of‐flight mass spectrometer coupled with a fast flow reactor. Hydrogen atom abstraction (HAA) from n‐butane by (Sc2O3)NO? (N=1–18) clusters was observed. The reactivity of (Sc2O3)NO? (N=1–18) clusters is significantly sizedependent and the highest reactivity was observed for N=4 (Sc8O13?) and 12 (Sc24O37?). Larger (Sc2O3)NO? clusters generally have higher reactivity than the smaller ones. Density functional theory calculations were performed to interpret the reactivity of (Sc2O3)NO? (N=1–5) clusters, which were found to contain the O?. radicals as the active sites. The local charge environment around the O?. radicals was demonstrated to control the experimentally observed size‐dependent reactivity. This work is among the first to report HAA reactivity of cluster anions with dimensions up to nanosize toward alkane molecules. The anionic O?. containing scandium oxide clusters are found to be more reactive than the corresponding cationic ones in the C?H bond activation.  相似文献   
960.
The application of metal–organic polyhedra as “molecular flasks” has precipitated a surge of interest in the reactivity and property of molecules within well‐defined spaces. Inspired by the structures of the natural enzymatic pockets, three metal–organic neutral molecular tetrahedral, Ce‐TTS, Ce‐TNS and Ce‐TBS (H6TTS: N′,N′′,N′′′‐nitrilotris‐4,4′,4′′‐(2‐hydroxybenzylidene)‐benzohydrazide; H6TNS: N′,N′′,N′′′‐nitrilotris‐6,6′,6′′‐(2‐hydroxybenzylidene)‐2‐naphthohydrazide; H6TBS: 1,3,5‐ phenyltris ‐4,4′,4′′‐(2‐hydroxybenzylidene)benzohydrazide), which exhibit different size of the edges and cavities, were achieved through self‐assembly by incorporating robust amide‐containing tridentate chelating sites into the fragments of the ligands. They acted as molecular flasks to prompt the cyanosilylation of aldehydes with excellent selectivity towards the substrates size. The amide groups worked as trigger sites and catalytic driven forces to achieve efficient guest interactions, enforcing the substrates proximity within the cavity. Experiments on catalysts with the different cavity radii and substrates with the different molecular size demonstrated that the catalytic performance exhibited enzymatical catalytic mechanism and occurred in the molecular flask. These amides were also able to amplify guest‐bonding events into the measurable outputs for the detection of concentration variations of the substrates, providing the possibility for metal–organic hosts to work as smart molecular flasks for the luminescent tracing of catalytic reactions.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号