全文获取类型
收费全文 | 70334篇 |
免费 | 10384篇 |
国内免费 | 6960篇 |
专业分类
化学 | 47694篇 |
晶体学 | 707篇 |
力学 | 4644篇 |
综合类 | 545篇 |
数学 | 8703篇 |
物理学 | 25385篇 |
出版年
2024年 | 61篇 |
2023年 | 1402篇 |
2022年 | 1463篇 |
2021年 | 2103篇 |
2020年 | 2617篇 |
2019年 | 2522篇 |
2018年 | 2251篇 |
2017年 | 2008篇 |
2016年 | 3063篇 |
2015年 | 3121篇 |
2014年 | 3707篇 |
2013年 | 4961篇 |
2012年 | 6100篇 |
2011年 | 6347篇 |
2010年 | 4307篇 |
2009年 | 4263篇 |
2008年 | 4419篇 |
2007年 | 3985篇 |
2006年 | 3696篇 |
2005年 | 3220篇 |
2004年 | 2580篇 |
2003年 | 1939篇 |
2002年 | 1622篇 |
2001年 | 1480篇 |
2000年 | 1357篇 |
1999年 | 1503篇 |
1998年 | 1295篇 |
1997年 | 1125篇 |
1996年 | 1185篇 |
1995年 | 1066篇 |
1994年 | 1006篇 |
1993年 | 862篇 |
1992年 | 762篇 |
1991年 | 663篇 |
1990年 | 554篇 |
1989年 | 482篇 |
1988年 | 364篇 |
1987年 | 350篇 |
1986年 | 296篇 |
1985年 | 301篇 |
1984年 | 203篇 |
1983年 | 176篇 |
1982年 | 147篇 |
1981年 | 115篇 |
1980年 | 84篇 |
1979年 | 51篇 |
1978年 | 56篇 |
1977年 | 53篇 |
1975年 | 57篇 |
1973年 | 59篇 |
排序方式: 共有10000条查询结果,搜索用时 78 毫秒
101.
A variety of heterobiaryl compounds have been synthesized by the Suzuki‐Miyaura coupling reactions of heteroaryl halides with potassium aryltrifluoroborates. Pd (OAc)2 was found to be highly efficient for the Suzuki‐Miyaura coupling reactions of various heteroaryl halides with potassium aryltrifluoroborates in aqueous systems, delivering the corresponding heterobiaryl compounds in good to excellent yields. 相似文献
102.
Cu‐doped Ni‐based metal–organic frameworks (MOFs) nanomaterials fabricated through a one‐pot hydrothermal reaction were characterized, and their performance as supercapacitor electrode materials was further studied for the first time. The results indicated that the doping of foreign metals and the introduction of K3[Fe(CN)6] in the KOH electrolyte significantly improve the performance of the supercapacitor. The results indicated that the Ni2.6Cu0.4 MOFs material shows the highest specific capacitance (1282 F g?1 at 1 A g?1 in mixed 2 M KOH and 0.1 M K3[Fe(CN)6]) and optimal capacitance retention (85.7% after 2000 cycles). This work provides a feasible optimization strategy for the construction of MOFs‐based supercapacitor electrode materials with excellent performance, and also provides a reliable experimental and theoretical basis for practical industrial production. 相似文献
103.
Liwei Chen Prof. Dr. Jinkee Hong Prof. Dr. Hans-Jürgen Butt Prof. Dr. Sanghyuk Wooh 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(18):4535-4542
Metal oxide photocatalysts (MOPCs) decompose organic molecules under illumination. However, the application of MOPCs in industry and research is currently limited by their intrinsic hydrophilicity because MOPCs can be wetted by most liquids. To achieve liquid repellency, the surface needs to possess a low surface energy, but most organic molecules with low surface energy are degraded by photocatalytic activity. Herein, current methods to achieve liquid repellency on MOPCs, while preventing degradation of hydrophobic coatings, are reviewed. Classically, composite materials containing MOPCs and hydrophobic organic compounds possess good liquid repellency. However, composites normally form irregular coatings and are hard to prepare on surfaces such as those that are mesoporous or nanostructured. In addition, the adhesion of composites to substrates is often weak, resulting in delamination. Recent studies have shown that the direct grafting reaction of polydimethylsiloxane (PDMS) from silicone oil (methyl-terminated PDMS) under illumination results in a stable polymer brush. This easy and simple grafting method allows us to create stable liquid-repellent surfaces on MOPCs of various types, structures, and sizes. In particular, super-liquid-repellent drops with an underlying air layer can be created on PDMS-grafted nano-/microstructured MOPCs. Potential applications of surfaces combining liquid repellency and photocatalytic activity are also discussed; thus offering new ways of using MOPCs in a wider range of applications. 相似文献
104.
The p‐arsanilic acid (p‐ASA), as an aromatic organoarsenic compounds, had received considerable concerns for their potential toxicity and carcinogenic properties. It was essential to detect p‐ASA with a facile method. In this paper, an europium based fluorescent metal–organic framework (MOF) [Eu2(clhex)·2H2O)]·H2O ( BUC‐69 ) was successfully prepared under hydrothermal conditions with 1,2,3,4,5,6‐cyclohexanehexacarboxylic acid (H6clhex) as organic linker. BUC‐69 displayed superior fluorescence capability to achieve selective and sensitive detection toward p‐ASA in water, which presented the first example of a MOF‐based sensor to detect p‐ASA. BUC‐69 showed excellent chemical stability in solutions under pH ranging from 4 to 12, which makes it be a potential sensor both in acidity and alkalinity condition. Significantly, BUC‐69 performed well in fluorescent sensing of p‐ASA at a low concentration (10?6 M) in the simulated wastewater prepared with real lake water, and the results were comparable to the values detected by Inductively Coupled Plasma Optical Emission Spectrometer (ICP‐OES). The corresponding mechanism of fluorescent sensing toward p‐ASA with BUC‐69 was proposed and affirmed. 相似文献
105.
Dr. Hongming He Qian-Qian Zhu Jia-Nan Zhao Dr. Hongming Sun Jing Chen Dr. Cheng-Peng Li Prof. Miao Du 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(49):11474-11480
CO2 is considered as the primary greenhouse gas, resulting in a series of serious environmental problems that affect people's life and health. Carbon capture and sequestration has been implemented as one of the most appealing pathways to control and use CO2. Here, we rationally integrate various functional sites within the confined nanospace of a microporous metal–organic framework (MOF) material, which is constructed by mixed-ligand strategy based on metal-adeninate vertices. It not only exhibits excellent stability but also can efficiently transform CO2 and epoxides to cyclic carbonates under mild and cocatalyst-free conditions. Additionally, this catalyst shows extraordinary recyclability for the CO2 cycloaddition reaction. 相似文献
106.
Wenjing Li Mingchun Lu Eva Zurek Xuedi Xu Lulu Chen Miao Zhang Lili Gao Xin Zhong Jia Li Xiaoming Zhou Wenyan Liu 《Physics letters. A》2019,383(10):1047-1051
Silicon (Si) is one of the most essential elements, as it is indispensable for modern electronic technology. The standard Si structure at ambient conditions is the cubic diamond structure, and it has an indirect band gap, which prevents it from being considered as a next-generation platform for semiconductor technologies. Therefore, the search for new allotropes of silicon has attracted great attention. Herein, first principles swarm-intelligence structure searches coupled with density-functional theory were performed to explore the stable high-pressure phases of silicon-rich lithium containing compounds, LiSix (). The LiSi4 stoichiometry was predicted to be stable, and it was found to assume one of the following space groups, P4/mnc, Cmmm, and C2/m within the pressure range of 0 to 50 GPa. By removing the Li atoms from these compounds, three silicon allotropes were obtained that were metastable at ambient pressures. Our work illustrates how novel silicon allotropes can be predicted using the CALYPSO method. 相似文献
107.
In this paper, we study polynomials orthogonal with respect to a Pollaczek–Jacobi type weight The uniform asymptotic expansions for the monic orthogonal polynomials on the interval (0,1) and outside this interval are obtained. Moreover, near , the uniform asymptotic expansion involves Airy function as , and Bessel function of order α as in the neighborhood of , the uniform asymptotic expansion is associated with Bessel function of order β as . The recurrence coefficients and leading coefficient of the orthogonal polynomials are expressed in terms of a particular Painlevé III transcendent. We also obtain the limit of the kernel in the bulk of the spectrum. The double scaled logarithmic derivative of the Hankel determinant satisfies a σ‐form Painlevé III equation. The asymptotic analysis is based on the Deift and Zhou's steepest descent method. 相似文献
108.
Jiatian Chen Le Yang Ying Li Qinghua Hou Lanlan Li Peng Jin 《International journal of quantum chemistry》2019,119(16):e25961
Inorganic planar ring-shape molecules with 4n + 2 π electrons are always the focus of experimental synthesis and theoretical research due to their potential aromaticity and stability. In this work, the whole series of five-membered heterocycle monoanions X nY5-n− (X, Y = group 15 elements; n = 1-4) were thoroughly investigated by means of density functional theory calculations. They all have large formation energies and HOMO-LUMO gap energies, suggesting the potential thermodynamic and kinetic stability. Their aromaticities are comparable to that of typical aromatic hydrocarbons. Their thermal stabilities were firmly established by the ab initio molecular dynamics simulations. As most of them are predicted for the first time, their various spectra were simulated for experimental characterization. Furthermore, we demonstrate that these five-membered cyclic anions can be employed as η5-ligand to construct novel all-inorganic metallocenes, which may serve as the building blocks of low-dimensional nanomaterials. 相似文献
109.
Zhipeng Lin Hao Zhang Guofeng Liang Yanqi Jin Hongbin Zeng Jiawang Li Jian Chen Weihong Zhang Fangyan Xie Yanshuo Jin Hui Meng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(12):3112-3118
A composite of FeOOH nanocubes anchored on carbon ribbons has been synthesized and used as a cathode material for Li/O2 batteries. Fe2+ ion-exchanged resin serves as a precursor for both FeOOH nanocubes and carbon ribbons, which are formed simultaneously. The as-prepared FeOOH cubes are proposed to have a core–shell structure, with FeOOH as the shell and Prussian blue as the core, based on information from XPS, TEM, and EDS mapping. As a cathode material for Li/O2 batteries, FeOOH delivers a specific capacity of 14816 mA h g−1cathode with a cycling stability of 67 cycles over 400 h. The high performance is related to the low overpotential of the oxygen reduction/evolution reaction on FeOOH. The cube structure, the supporting carbon ribbons, and the -OOH moieties all contribute to the low overpotential. The discharge product Li2O2 can be efficiently decomposed in the FeOOH cathode after a charging process, leading to higher cycling stability. Its high activity and stability make FeOOH a good candidate for use in non-aqueous Li/O2 batteries. 相似文献
110.
Xiaoyu Ding Dr. Zhenghui Pan Na Liu Linge Li Xianshu Wang Guoguang Xu Jie Yang Jin Yang Nengsheng Yu Meinan Liu Prof. Wanfei Li Prof. Yuegang Zhang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(15):3775-3780
Flexible lithium/sulfur (Li/S) batteries are promising to meet the emerging power demand for flexible electronic devices. The key challenge for a flexible Li/S battery is to design a cathode with excellent electrochemical performance and mechanical flexibility. In this work, a flexible strap-like Li/S battery based on a S@carbon nanotube/Pt@carbon nanotube hybrid film cathode was designed. It delivers a specific capacity of 1145 mAh g−1 at the first cycle and retains a specific capacity of 822 mAh g−1 after 100 cycles. Moreover, the flexible Li/S battery retains stabile specific capacity and Coulombic efficiency even under severe bending conditions. As a demonstration of practical applications, an LED array is shown stably powered by the flexible Li/S battery under flattened and bent states. We also use the strap-like flexible Li/S battery as a real strap for a watch, which at the same time provides a reliable power supply to the watch. 相似文献