全文获取类型
收费全文 | 16652篇 |
免费 | 2390篇 |
国内免费 | 5246篇 |
专业分类
化学 | 21025篇 |
晶体学 | 149篇 |
力学 | 441篇 |
综合类 | 165篇 |
数学 | 167篇 |
物理学 | 2341篇 |
出版年
2024年 | 31篇 |
2023年 | 273篇 |
2022年 | 541篇 |
2021年 | 731篇 |
2020年 | 1146篇 |
2019年 | 968篇 |
2018年 | 776篇 |
2017年 | 732篇 |
2016年 | 849篇 |
2015年 | 871篇 |
2014年 | 1049篇 |
2013年 | 1563篇 |
2012年 | 1173篇 |
2011年 | 1094篇 |
2010年 | 891篇 |
2009年 | 933篇 |
2008年 | 1023篇 |
2007年 | 1004篇 |
2006年 | 1009篇 |
2005年 | 906篇 |
2004年 | 935篇 |
2003年 | 825篇 |
2002年 | 601篇 |
2001年 | 551篇 |
2000年 | 487篇 |
1999年 | 376篇 |
1998年 | 362篇 |
1997年 | 395篇 |
1996年 | 310篇 |
1995年 | 357篇 |
1994年 | 294篇 |
1993年 | 316篇 |
1992年 | 229篇 |
1991年 | 132篇 |
1990年 | 122篇 |
1989年 | 87篇 |
1988年 | 72篇 |
1987年 | 62篇 |
1986年 | 35篇 |
1985年 | 35篇 |
1984年 | 24篇 |
1983年 | 16篇 |
1982年 | 21篇 |
1981年 | 19篇 |
1980年 | 17篇 |
1979年 | 13篇 |
1978年 | 6篇 |
1977年 | 4篇 |
1976年 | 8篇 |
1973年 | 5篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
1.
合成了一种多级孔芳香骨架材料(PAF-70); 使用由氨基修饰过的单体, 应用该合成策略得到了同样具有窄分布介孔的含有氨基活性位点的PAF材料, 并通过硫脲单体与其氨基活性位点的反应, 将硫脲基团引入PAF-70材料中, 获得了含有硫脲催化位点的材料(PAF-70-thiourea). 氮气吸附-脱附测试结果显示, PAF-70存在孔径分布较窄的介孔, 介孔孔径为3.8 nm, 与模拟计算值(约3.7 nm)吻合. 热重分析结果表明, PAF-70具有很高的热稳定性. PAF-70在大多数溶剂中可以稳定存在, 具有良好的化学稳定性. 将PAF-70-thiourea作为催化剂, 应用在N-溴代琥珀酰亚胺(NBS)氧化醇类的反应中, 其表现出较高的催化活性、 较高的稳定性和广泛的底物适用性. 与含有相同硫脲催化位点的金属有机框架(MOF)材料(IRMOF-3-thiourea)作为催化剂对比, 进一步证实PAFs材料非常适合作为催化有机反应的固载平台. 相似文献
2.
Superconductivity and unconventional density waves in vanadium-based kagome materials AV3Sb5 下载免费PDF全文
Recently, the discovery of vanadium-based kagome metal AV3Sb5 (A= K, Rb, Cs) has attracted great interest in the field of superconductivity due to the coexistence of superconductivity, non-trivial surface state and multiple density waves. In this topical review, we present recent works of superconductivity and unconventional density waves in vanadium-based kagome materials AV3Sb5. We start with the unconventional charge density waves, which are thought to correlate to the time-reversal symmetry-breaking orders and the unconventional anomalous Hall effects in AV3Sb5. Then we discuss the superconductivity and the topological band structure. Next, we review the competition between the superconductivity and charge density waves under different conditions of pressure, chemical doping, thickness, and strains. Finally, the experimental evidence of pseudogap pair density wave is discussed. 相似文献
3.
《Mendeleev Communications》2022,32(1):105-108
A mixed-metal 1D coordination polymer [CaCu(HBTC)2(H2O)8]n (where H3BTC – benzene-1,3,5-tric arboxylic acid) was obtained in a solvothermal synthesis of a well-known copper-containing metal–organic framework [Cu3(BTC)2(H2O)3]n (HKUST-1) in autoclaves 3D-printed from commercial polypropylene. This material was a source of calcium ions, apparently, leaking from a colorant (calcium carbonate) promoted by glacial acetic acid as a modulator used to produce large single crystals of HKUST-1. This finding was confirmed by elemental analysis and a model experiment that resulted in a new calcium-based 1D coordination polymer [Ca(H2BTC)2(H2O)5]n under the same solvothermal conditions with no copper or calcium salts put into a 3D-printed autoclave. 相似文献
4.
Xianghao Luo Anqi Tian Mengyu Pei Dr. Jiaying Yan Dr. Xiang Liu Prof. Long Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(3):e202103361
With the development of green chemistry, it is still a challenge to maintain the unstable valence state of the metal in heterogeneous catalysts and realize new catalytic synthesis methods. In this paper, it is reported that an univalent copper nanocomposite (Cu@Al/SBA-15) can efficiently catalyze the formation of novel amino-containing benzotriazoles with great fluorescence properties in a new synthetic strategy. Subsequently, its application is further verified by an acylation reaction to produce a series of novel benzotriazoles derivatives with high yield. It is worth noting that the Cu@Al/SBA-15 nanocomposites not only enable the reaction completed with high yield in a short time, but can also be recycled many times without a significant reduction in activity, and the leaching of copper and aluminum species in reaction system is negligible. Finally, the detailed and feasible reaction mechanism is also provided. 相似文献
5.
Dr. Yoko Hasegawa Dr. Thomas Cantin Dr. Jonathan Decaens Dr. Samuel Couve-Bonnaire Prof. Dr. André B. Charette Prof. Dr. Thomas Poisson Prof. Dr. Philippe Jubault 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(47):e202201438
The first diastereo- and enantioselective cyclopropanation reactions of electron-deficient allenes with donor-acceptor and diacceptor diazo reagents are described. The desired enantioenriched alkylidenecyclopropanes (ACPs) were obtained in high yields with high diastereo- and enantioselectivities in the presence of Rh2((S)-TCPTAD)4 or Rh2((R)-BTPCP)4 catalysts (up to 95 % yield, >95 : 5 d.r. and 99 : 1 e.r.). This methodology gave a direct access to ACPs bearing multiple electron-deficient substituents and allows to further expand the availability of ACPs chemistry. Interestingly, during the examination of the scope of this reaction, the asymmetric intramolecular C−H insertion reaction into tert-butyl group was observed as a side reaction with up to 94 : 6 e.r. 相似文献
6.
Photocatalytic CO2 reduction to C1 fuels is considered to be an important way for alleviating increasingly serious energy crisis and environmental pollution. Due to the environment-friendly, simple preparation, easy formation of highly-stable metal-nitrogen(M-Nx) coordination bonds, and suitable band structure, polymeric carbon nitride-based single-atom catalysts(C3N4-based SACs) are expected to become a potential for CO2 reduction under visible-light irradiation. In this review, we summarize the recent advancement on C3N4-based SACs for photocatalytic CO2 reduction to C1 products, including the reaction mechanism for photocatalytic CO2 reduction to C1 products, the structure and synthesis methods of C3N4-based SACs and their applications toward photocatalytic CO2 reduction reaction(CO2RR) for C1 production. The current challenges and future opportunities of C3N4-based SACs for photoreduction of CO2 are also discussed. 相似文献
7.
Peng Zhou Yang Yi Dr. Yuan-Zhao Hua Dr. Shi-Kun Jia Prof. Dr. Min-Can Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(2):e202103688
The application of dinuclear zinc catalysts in a dearomatization reaction has been developed. Catalytic asymmetric dearomatization [3+2] annulations of 2-nitrobenzofurans or 2-nitrobenzothiophenes with CF3-containing N-unprotected isatin-derived azomethine ylides catalyzed by dinuclear zinc catalysts are realized with excellent diastereomer ratios (dr) of >20 : 1 and enantiomeric excess (ee) of up to 99 %. This protocol provides a practical, straightforward access to structurally diverse pyrrolidinyl spirooxindoles containing a 2,3-fused-dihydrobenzofuran (or dihydrobenzothiphene) moiety, and four contiguous stereocenters. Reactions can be performed on a gram scale. The absolute configuration of products is confirmed by X-ray single crystal structure analysis, and a possible mechanism is proposed. 相似文献
8.
通过3,3′-((乙烷-1,2-二基双(2-甲基吡啶杂氮二基)双(亚甲基))双(2-羟基-5-甲基苯甲醛)与2-羟基-1,3-丙二胺的缩合反应得到一种具有双吡啶悬臂的双核锰配合物。通过X射线单晶衍射确定了该配合物结构,结果显示其分子式为[Mn2(C37H43N6O6)]·(ClO4)2。该配合物属于单斜晶系,P21/c空间群,晶胞参数为:a=1.096 50(19) nm, b=1.419 5(3) nm, c=3.109 4(5) nm, β=108.153(5)°。进一步分析表明两个二价锰离子分别与(Namine)2(Nimine)2O3和(Nimine)2O4体系配位,它们与配位原子形成的几何构型分别是十面体和扭曲的八面体。两个中心锰离子距离为0.331 6 nm,由酚氧原子和醋酸根共同桥联。另外,本文也利用伏安法和黏度法对该配合物与小牛胸腺DNA的结合能力进行研究,实验结果表明它们之间的结合方式为弱的插入作用。 相似文献
9.
10.
Wacker oxidation is an industry-adopted process to transform olefins into value-added epoxides and carbonyls. However, traditional Wacker oxidation involves the use of homogeneous palladium and copper catalysts for the olefin addition and reductive elimination. Here, we demonstrated an ultrahigh loading Cu single atom catalyst(14% Cu, mass fraction) for the palladium-free Wacker oxidation of 4-vinylanisole into the corresponding ketone with N-methylhydroxylamine hydrochloride as an additive under mild conditions. Mechanistic studies by 18O and deuterium isotope labelling revealed a hydrogen shift mechanism in this palladium-free process using N-methylhydroxylamine hydrochloride as the oxygen source. The reaction scope can be further extended to Kucherov oxidation. Our study paves the way to replace noble metal catalysts in the traditional homogeneous processes with single atom catalysts. 相似文献