全文获取类型
收费全文 | 43483篇 |
免费 | 7916篇 |
国内免费 | 5116篇 |
专业分类
化学 | 30146篇 |
晶体学 | 597篇 |
力学 | 2788篇 |
综合类 | 371篇 |
数学 | 5208篇 |
物理学 | 17405篇 |
出版年
2024年 | 45篇 |
2023年 | 944篇 |
2022年 | 1035篇 |
2021年 | 1412篇 |
2020年 | 1860篇 |
2019年 | 1741篇 |
2018年 | 1527篇 |
2017年 | 1419篇 |
2016年 | 2099篇 |
2015年 | 2059篇 |
2014年 | 2481篇 |
2013年 | 3179篇 |
2012年 | 3850篇 |
2011年 | 4037篇 |
2010年 | 2800篇 |
2009年 | 2724篇 |
2008年 | 2892篇 |
2007年 | 2602篇 |
2006年 | 2438篇 |
2005年 | 1926篇 |
2004年 | 1559篇 |
2003年 | 1304篇 |
2002年 | 1195篇 |
2001年 | 975篇 |
2000年 | 970篇 |
1999年 | 907篇 |
1998年 | 796篇 |
1997年 | 743篇 |
1996年 | 757篇 |
1995年 | 681篇 |
1994年 | 590篇 |
1993年 | 469篇 |
1992年 | 457篇 |
1991年 | 367篇 |
1990年 | 341篇 |
1989年 | 261篇 |
1988年 | 223篇 |
1987年 | 189篇 |
1986年 | 164篇 |
1985年 | 164篇 |
1984年 | 104篇 |
1983年 | 73篇 |
1982年 | 66篇 |
1981年 | 41篇 |
1980年 | 20篇 |
1979年 | 10篇 |
1977年 | 2篇 |
1971年 | 2篇 |
1959年 | 2篇 |
1957年 | 5篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
81.
Alkynes cycloaddition reactions are powerful tools for constructing cyclic molecules with optimal atom efficiency, but these reactions cannot proceed at ambient temperature without transition-metal catalysts. In this work, a heterobimetallic complex featuring an Nb–Fe triple bond, Nb(iPrNPMe2)3Fe–PMe3, has been evaluated as the potential catalyst for acetylene cycloaddition, using density functional theory. The calculated results show that the singlet-state (i.e. ground-state) Nb(iPrNPMe2)3Fe–PMe3 can be applied to benzene synthesis, but is not suitable for cyclobutadiene. Benzene can be obtained easily at room temperature and is the unique product on the singlet potential surface. The irradiation of infrared-red light can drive the excitation of singlet Nb(iPrNPMe2)3Fe–PMe3 to its triplet state. Both benzene and cyclobutadiene can be formed on the triplet reaction potential surface due to their low energy barriers. Therefore, Nb(iPrNPMe2)3Fe–PMe3 is a potential high reactivity heterobimetallic catalyst for the cyclotrimerization of alkynes. In the reaction process, the catalytic active site of Nb(iPrNPMe2)3Fe–PMe3 moves from niobium to iron. 相似文献
82.
A novel metal-doped metal–organic framework (MOF) was developed by incorporating salen–Mg into NH2–MIL-101(Cr) structure under ambient conditions. The Schiff base complex was successfully prepared by condensing salicylaldehyde with a free amino group and then coordinating metal ions. Such a structure can endow the sample with higher CO2 adsorption performance. At 0°C and 1 bar, the salen–Mg-modified sample achieves the maximum adsorption capacity of 2.18 mmol g−1 for CO2, which was 5.8% higher than the pristine salen–MOF under the same conditions. Notably, the Freundlich model indicates that the CO2 adsorption process of all samples conforms to reversible adsorption. However, the correlation coefficients (R2) of the Mg-doped sample are lower than that of the pristine sample. Besides, the CO2/N2 adsorption selectivity and isosteric heat also show a similar trend. These results indicate that the salen–Mg can enhance the interaction between the material and CO2 molecules. 相似文献
83.
Wenyuan Xu Yan Wang Suying Li Yongbing Cheng Zanru Guo Lin Hu Mengyin Liao Jiaxi Peng Xi Chen Shaoming Yang 《应用有机金属化学》2021,35(1)
Dimethyldichlorosilane, one of the most consumed organosilicon monomers in the industry, can be prepared in a highly efficient and environmentally friendly synthesis method of disproportionating methylchlorosilanes. However, the internal mechanism of the reaction remains unclear. In this paper, the mechanism catalyzed by AlCl3/MIL‐53(Al) and AlCl3/MIL‐53(Al)@γ‐Al2O3 catalysts was calculated at B3LYP/6‐311++G(3df, 2pd) level by using the density functional theory (DFT). The results showed that although the two catalysts had similar active structures, the catalytic effects were significantly different. The Lewis acid center on the surface of γ‐Al2O3 in the core‐shell catalyst is complementary to the classic Lewis acid AlCl3 through the spatial superposition effect, which greatly improves the Lewis acid catalytic activity of AlCl3/MIL‐53(Al)@γ‐Al2O3. 相似文献
84.
85.
钙钛矿稀土正铁氧体RFeO3具有丰富的磁性,这主要源于4f电子层的稀土离子和3d电子层的铁离子之间复杂的相互作用。磁化跃迁作为RFeO3体系中的重要现象,是指体系中的稀土离子磁矩和铁离子磁矩在特定的磁场和温度下发生180°旋转,宏观表现为磁热曲线中磁化强度发生断崖式变化。本文综述了不同化合物RFeO3的两种磁化跃迁现象,第一类磁化跃迁通常具有补偿点,FR与FFe的排列耦合方向不变,第二类磁化跃迁则相反,且两类磁化跃迁出现的温区受外加磁场的调控。 相似文献
86.
Yu Ming Fu Yalu Liu Pengxin Tang Zhigong Yuan Xianxu Xu Chunxiao 《Acta Mechanica Sinica》2022,38(9):1-16
Acta Mechanica Sinica - Bogies are responsible for a significant amount of aerodynamic resistance and noise, both of which negatively affect high-speed train performance and passenger comfort. In... 相似文献
87.
Shengjie Li Yangdong Xu Manxue You Shengkun Zhu 《Journal of Optimization Theory and Applications》2018,177(3):609-636
Image space analysis is a new tool for studying scalar and vector constrained extremum problems as well as generalized systems. In the last decades, the introduction of image space analysis has shown that the image space associated with the given problem provides a natural environment for the Lagrange theory of multipliers and that separation arguments turn out to be a fundamental mathematical tool for explaining, developing and improving such a theory. This work, with its 3 parts, aims at contributing to describe the state-of-the-art of image space analysis for constrained optimization and to stress that it allows us to unify and generalize the several topics of optimization. In this 1st part, after a short introduction of such an analysis, necessary and sufficient optimality conditions are treated. Duality and penalization are the contents of the 2nd part. The 3rd part deals with generalized systems, in particular, variational inequalities and Ky Fan inequalities. Some further developments are discussed in all the parts. 相似文献
88.
The elementometalation process is a fundamental chemical step in several catalytic cycles. In this work, density functional theory computations have elucidated the detailed elementometalation mechanism of activated alkyne RCCR(RCO2Me) by Cp2TaH3 and rationalized the selectivity in experimental findings. The calculated results show that in the formation process of (E)-olefin monohydride((E)-Pro), the Gibbs free energy barrier is low and the entire reaction is spontaneous and exothermic; thus, (E)-Pro can be formed easily. The formation of (Z)-η2-olefin monohydride complex ((Z)-Pro) is difficult due to its high Gibbs free energy barrier. The formation process (E)-Pro consists of the following five steps: hydride H1-shift, conformational isomerism 1, hydride H2-shift, conformational isomerism 2, and olefin coordination process. Topological analysis shows that there is a five-membered ring plane structure in the reaction pathway and that the final product (E)-Pro belongs to a typical η2-olefin monohydride complex. Our calculated results provide an explanation for experimental observations and useful insights for further development of olefin functionalization. © 2019 Wiley Periodicals, Inc. 相似文献
89.
Cuixia Cui Yong Gao Dr. Jun Li Chao Yang Meng Liu Prof. Dr. Huile Jin Prof. Dr. Zhenhai Xia Prof. Dr. Liming Dai Prof. Dr. Yong Lei Prof. Dr. Jichang Wang Prof. Dr. Shun Wang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(20):8002-8007
Although tremendous efforts have been devoted to understanding the origin of boosted charge storage on heteroatom-doped carbons, none of the present studies has shown a whole landscape. Herein, by both experimental evidence and theoretical simulation, it is demonstrated that heteroatom doping not only results in a broadened operating voltage, but also successfully promotes the specific capacitance in aqueous supercapacitors. In particular, the electrolyte cations adsorbed on heteroatom-doped carbon can effectively inhibit hydrogen evolution reaction, a key step of water decomposition during the charging process, which broadens the voltage window of aqueous electrolytes even beyond the thermodynamic limit of water (1.23 V). Furthermore, the reduced adsorption energy of heteroatom-doped carbon consequently leads to more stored cations on the heteroatom-doped carbon surface, thus yielding a boosted charge storage performance. 相似文献
90.
采用水热法制备花状Bi2 WO6,并利用超声分散法制备了Cu2 O/TiO2-Bi2 WO6复合光催化剂,通过FESEM、XRD、XPS、FI-IR、UV-vis DRS和PL对光催化剂进行了分析和表征.表征结果证明:花状Bi2 WO6表面负载着碎片状的TiO2和立方体Cu2 O形成Cu2 O/TiO2-Bi2 WO6复合光催化剂;以短链脂肪酸(SCFAs)为牺牲剂,考察复合光催化剂的光催化产生氢气和烷烃的性能.实验结果表明:Cu2 O/TiO2-Bi2 WO6复合光催化剂以乙酸为牺牲剂,主要产氢气和甲烷,降解率高达91.82;;以丙酸为牺牲剂,产物主要是乙烷和丁烷,降解率高达90.70;;以丁酸为牺牲剂,除了氢气,甲烷,乙烷,丙烷,丁烷外,气体产物还含有一定量的戊烷,其降解率高达91.50;.结合反应液中间产物的成分进行检测,由此推断出光催化反应的可能机理. 相似文献