全文获取类型
收费全文 | 29827篇 |
免费 | 3952篇 |
国内免费 | 6877篇 |
专业分类
化学 | 27223篇 |
晶体学 | 692篇 |
力学 | 1290篇 |
综合类 | 281篇 |
数学 | 2211篇 |
物理学 | 8959篇 |
出版年
2024年 | 36篇 |
2023年 | 315篇 |
2022年 | 590篇 |
2021年 | 946篇 |
2020年 | 1294篇 |
2019年 | 1043篇 |
2018年 | 926篇 |
2017年 | 1024篇 |
2016年 | 1225篇 |
2015年 | 1088篇 |
2014年 | 1416篇 |
2013年 | 2866篇 |
2012年 | 2478篇 |
2011年 | 1795篇 |
2010年 | 1426篇 |
2009年 | 1837篇 |
2008年 | 1936篇 |
2007年 | 1993篇 |
2006年 | 1945篇 |
2005年 | 1795篇 |
2004年 | 1715篇 |
2003年 | 1441篇 |
2002年 | 1177篇 |
2001年 | 919篇 |
2000年 | 929篇 |
1999年 | 766篇 |
1998年 | 656篇 |
1997年 | 621篇 |
1996年 | 597篇 |
1995年 | 607篇 |
1994年 | 568篇 |
1993年 | 446篇 |
1992年 | 459篇 |
1991年 | 347篇 |
1990年 | 272篇 |
1989年 | 216篇 |
1988年 | 171篇 |
1987年 | 137篇 |
1986年 | 132篇 |
1985年 | 102篇 |
1984年 | 89篇 |
1983年 | 35篇 |
1982年 | 58篇 |
1981年 | 44篇 |
1980年 | 32篇 |
1979年 | 27篇 |
1978年 | 19篇 |
1977年 | 17篇 |
1976年 | 16篇 |
1973年 | 29篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
51.
CHEN Jianfei CHEN Xiaoyu ZHANG Xing YUAN Yao BI Ruyi YOU Feifei WANG Zumin YU Ranbo 《高等学校化学研究》2020,36(1):120-126
BiVO4,a promising visible-light responding photocatalyst,has aroused extensive research interest because of inexpensiveness and excellent chemical stability.However,its main drawback is the poor photoinduced charge-transfer dynamics.Building nanostructures is an effective way to tackle this problem.Herein,we put forward a new method to prepare nanostructured BiVO4 from Bi-based metal-organic frameworks[Bi-MOF(CAU-17)]precursor.The as-prepared material has a rod-like morphology inherited from the Bi-MOF sacrificial template and consists of small nanoparticle as building blocks.Compared with its counterparts prepared by conventional methods,MOF-derived nanostructured BiVO4 shows better light absorption ability,narrower bandgap,and improved electrical conductivity as well as reduced recombination.Consequently,BiVO4 nanostructure demonstrates high photocatalytic activity under visible light towards the degradation of methylene blue.Methylene blue can be degraded up to 90%within 30 min with a reaction rate constant of 0.058 min-1.Moreover,the cycling stability of the catalyst is excellent to withstand unchanged degradation efficiency for at least 5 cycles. 相似文献
52.
Wei Wei Shu-Hua Yang Ze-Han Bao Chong Zhang Chang Gao Wei-Ru Fan 《中国物理C(英文版)》2020,44(9):094104-094104-10
53.
Qi-Jun Li Ya-Jie Ren Qin Xie Min Wu Hua-Xing Feng Li-Mei Zheng Hua-Xin Zhang Jin-Qiao Long Tian-Shun Wang 《应用有机金属化学》2020,34(10):e5813
Two nickel complexes, [Ni(tpen)](ClO4)2.0.5CH3COCH3 ( 1 ) and [Ni(tpbn)](ClO4)2 ( 2 ), of tetrapyridyl ligands N,N,N′,N′-tetrakis(2-pyridyl-methyl)-1,2-ethanediamine (tpen) and N,N,N′,N′-tetrakis(2-pyridyl-methyl)-1,4-butanediamine (tpbn) were prepared and their catalysis for water oxidation reaction (WOR) studied. In 0.1 M phosphate buffer solution (PBS) of pH 8.0, complex 1 is a homogeneous molecular catalyst with an overpotential of ~440 mV and a Faradaic efficiency of 89%. At pH ≥ 9.0, complex 1 degraded gradually during the catalytic process and formed NiOx composite (nickel oxide with general formula NixOyHz) active for WOR. In contrast, complex 2 deteriorated under measured conditions (pH 8.0–12.0) and formed NiOx composite active for WOR. The NiOx composite derived from 1 in 0.1 M PBS at pH 11.0 showed an activity with an overpotential of ~500 mV, a Tafel slope of ~90 mV/decade and a Faradaic efficiency of 97%. Mechanisms were proposed for water oxidation catalyzed by 1 and 2 . This work revealed that the catalytic activity of the nickel complexes was related to the flexibility of the tetrapyridyl ligands and the adaptability of the coordination sphere of the nickel(II) center. 相似文献
54.
Two new divalent copper (C1) and zinc (C2) chelates having the formulae [M(PIMC)2] (where M = Cu(II), Zn(II) and PIMC = Ligand [(E)-3-(((3-hydroxypyridin-2-yl)imino)methyl)-4H-chromen-4-one] were obtained and characterized by several techniques. Structures and geometries of the synthesized complexes were judged based on the results of alternative analytical and spectral tools supporting the proposed formulae. IR spectral data confirmed the coordination of the ligands to the copper and zinc centers as monobasic tridentate in the enol form. Thermal analysis, UV-Vis spectra and magnetic moment confirmed the geometry around the copper center to be tetrahedral, square pyramidal and octahedral. Study of the binding ability of the synthesized compounds with Circulating tumor DNA (CT-DNA) bas been evaluated applying UV-Vis spectral titration and viscosity measurements. The copper and zinc oxides were achieved from the copper and zinc nano-particles structures Schiff base complexes as the raw material after calcination for 5 hr at 600°C. On the other hand, synthesized of C1 and C2 NPs were used as suitable precursors to the preparation of CuO and ZnO NPs. Finally, the synthesized of the two complexes exhibited enhanced activity against the tested bacterial (Staphylococcus aureus and Escherichia Coli) and fungal strains (Candida albicans and Aspergillus fumigatus) as compared to HPIMC. Among all these synthesized compounds, C1 exhibits good cleaving ability compared to other newly synthesized C2. 相似文献
55.
Liming Fan Feng Wang Dongsheng Zhao Yuxin Peng Yuxin Deng Yinwei Luo Xiutang Zhang 《应用有机金属化学》2020,34(12):e5960
Guided by the self-penetrating features can improve the stability of metal organic frameworks (MOFs), an unprecedented 3D self-penetrated framework, {[Zn (tptc)0.5(bimb)]·H2O}n ( NUC-6 , here NUC corresponding to North University of China), with 3D (4,4)-c {86} net, was designed. Benefit from the high chemical stability and excellent luminescent property, NUC-6 can be act as an efficient multi-response chemo-sensor in detecting dichloronitroaniline pesticide and nitrofuran antibiotics in water with the detection limits are 116 ppb for DCN pesticide, 16 ppb for NFT antibiotic, and 12 ppb for NTZ antibiotic. Besides, the mechanisms of luminescence quenching were revealed from the viewpoint of internal filter effect (IFE) and photo-induced electron transfer (PET), implied by the optical spectroscopy and quantum chemical calculation. This work provides a promising strategy to design stable MOFs by improving the self-penetrating features and to expand their practical applications in the detection of organic pollutants in aqueous medium. 相似文献
56.
Florian Molton 《Magnetic resonance in chemistry : MRC》2020,58(8):718-726
Solid-state continuous wave (cw) electronic paramagnetic resonance (EPR) spectroscopy is particularly suitable for metal complex analysis. Extracting magnetic parameters by simulation is often necessary to describe the electronic structure of the studied molecular compounds that can have various electronic spin states and characterized by different parameters like g-values, hyperfine coupling or zero field splitting values. Easyspin toolbox on MATLAB is a powerful tool, but for the user, it requires spending time with coding and could discourage nonexperts. Facing this context, we have developed a graphical user interface called Simultispin, dedicated to solid-state cw-EPR spectra simulation. Some examples of experimental spectra of metal complexes (mixture of low spin and high spin FeIII complexes, dynamic disorder of a CuII complex, photogeneration of a MnIII complex), highlighting specific solid-state functions, are described and analyzed based on simulations performed with Simultispin. We hope that its ergonomy and the ease to set up a complete set of parameters to get reliable simulations could help a large EPR community to improve the efficiency of their interpretations. 相似文献
57.
Qianwen Deng Zhen Tian Xiaomin Wang Zhewei Yang Yucheng Wu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(3):650-658
Zinc–cobalt double-metal sulfides (ZCS) as Faradic electrode materials with high energy density have great potential for supercapacitors, but their poor transfer efficiency for electrons and ions hinders their electrochemical response. Herein, ZnCo2(CO3)1.5(OH)3@ZCS microflower hybrid arrays consisting of thin nanolayer petals were anchored on three-dimensional graphene (ZnCo2(CO3)1.5(OH)3@ZCS/3DG) by a simple hydrothermal method and additional ion-exchange process. A ZnCo2(CO3)1.5(OH)3@ZCS/3DG electrode delivered high capacitance (2228 F g−1 at 1 A g−1) and long cycling life (85.7 % retention after 17 000 cycles), which are ascribed to the multicomponent structural design. The 3DG conductive substrate improves the electron-transfer dynamics of the electrode material. Meanwhile, the microflowers consisting of thin nanolayer petals could not only provide many active sites for ions to improve the capacitance, but also alleviate the volume expansion to ensure the structural stability. Furthermore, an all-solid-state asymmetric supercapacitor based on a ZnCo2(CO3)1.5(OH)3@ZCS/3DG electrode achieved a high energy density of 27 W h kg−1 at 528.3 W kg−1 and exhibits exceptional cyclic stability for 23 000 cycles. Its ability to light a blue LED for 9 min verified the feasibility of its application for energy storage devices. 相似文献
58.
Laurens D. B. Mandemaker Miguel Rivera-Torrente Guusje Delen Dr. Jan P. Hofmann Dr. Matthias Lorenz Dr. Alex Belianinov Prof. Dr. Bert M. Weckhuysen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(3):691-698
Metal–organic frameworks (MOFs) are a promising class of materials for many applications, due to their high chemical tunability and superb porosity. By growing MOFs as (thin-)films, additional properties and potential applications become available. Here, copper (II) 1,3,5-benzenetricarboxylate (Cu-BTC) metal–organic framework (MOF) thin-films are reported, which were synthesized by spin-coating, resulting in “nanowebs”, that is, fiber-like structures. These surface-mounted MOFs (SURMOFs) were studied by using photoinduced force microscopy (PiFM) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The optimal concentration of precursors (10 mm ) was determined that resulted in chemically homogeneous, pure nanowebs. Furthermore, the morphology and (un)coordinated Cu sites in the web were tuned by varying the rotation speed of the spin-coating process. X-ray diffraction (XRD) analysis showed that rotation speeds ≥2000 rpm (with precursors in a water/ethanol solution) generate the catena-triaqua-μ-(1,3,5-benzenetricarboxylate)-copper(II), or Cu(BTC)(H2O)3 coordination polymer. X-ray photoelectron spectroscopy (XPS) highlighted the strong decrease in number of (defective) Cu+ sites, as the nanowebs mainly consist of coordinated Cu2+ Lewis acid sites (LAS) and organic linker–linker, for example, hydrogen-bonding, interactions. Finally, the Lewis-acidic character of the Cu sites is illustrated by testing the films as catalysts in the isomerization of α-pinene oxide. The higher number of LAS (≥3000 rpm), result in higher campholenic aldehyde selectivity reaching up to 87.7 %. Furthermore, the strength of a combined micro- and spectroscopic approach in understanding the nature of MOF thin-films in a spatially resolved manner is highlighted. 相似文献
59.
Dr. Haixiang Han Jesse C. Carozza Audra P. Colliton Yuxuan Zhang Dr. Zheng Wei Dr. Alexander S. Filatov Prof. Dr. Yu-Sheng Chen Melisa Alkan Prof. Dr. Andrey Yu. Rogachev Prof. Dr. Evgeny V. Dikarev 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(24):9711-9717
A known trinuclear structure was used to design the heterobimetallic mixed-valent, mixed-ligand molecule [CoII(hfac)3−Na−CoIII(acac)3] ( 1 ). This was used as a template structure to develop heterotrimetallic molecules [CoII(hfac)3−Na−FeIII(acac)3] ( 2 ) and [NiII(hfac)3−Na−CoIII(acac)3] ( 3 ) via isovalent site-specific substitution at either of the cobalt positions. Diffraction methods, synchrotron resonant diffraction, and multiple-wavelength anomalous diffraction were applied beyond simple structural investigation to provide an unambiguous assignment of the positions and oxidation states for the periodic table neighbors in the heterometallic assemblies. Molecules of 2 and 3 are true heterotrimetallic rather than a statistical mixture of two heterobimetallic counterparts. Trinuclear platform 1 exhibits flexibility in accommodating a variety of di- and trivalent metals, which can be further utilized in the design of molecular precursors for the NaMM′O4 functional oxide materials. 相似文献
60.
Congcong Pei Dr. Chao Liu Dr. You Wang Dan Cheng Rongxin Li Weikang Shu Chaoqi Zhang Wenli Hu Dr. Aihua Jin Dr. Yannan Yang Prof. Jingjing Wan 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(27):10923-10927
High-throughput metabolic analysis is of significance in diagnostics, while tedious sample pretreatment has largely hindered its clinic application. Herein, we designed FeOOH@ZIF-8 composites with enhanced ionization efficiency and size-exclusion effect for laser desorption/ionization mass spectrometry (LDI-MS)-based metabolic diagnosis of gynecological cancers. The FeOOH@ZIF-8-assisted LDI-MS achieved rapid, sensitive, and selective metabolic fingerprints of the native serum without any enrichment or purification. Further analysis of extracted serum metabolic fingerprints successfully discriminated patients with gynecological cancers (GCs) from healthy controls and also differentiated three major subtypes of GCs. Given the low cost, high-throughput, and easy operation, our approach brings a new dimension to disease analysis and classification. 相似文献