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   24667篇
  免费   4016篇
  国内免费   2365篇
化学   17264篇
晶体学   299篇
力学   1511篇
综合类   113篇
数学   2910篇
物理学   8951篇
  2024年   11篇
  2023年   495篇
  2022年   536篇
  2021年   738篇
  2020年   1003篇
  2019年   978篇
  2018年   797篇
  2017年   707篇
  2016年   1167篇
  2015年   1109篇
  2014年   1309篇
  2013年   1754篇
  2012年   2359篇
  2011年   2415篇
  2010年   1592篇
  2009年   1509篇
  2008年   1654篇
  2007年   1513篇
  2006年   1371篇
  2005年   1162篇
  2004年   851篇
  2003年   629篇
  2002年   569篇
  2001年   417篇
  2000年   411篇
  1999年   500篇
  1998年   410篇
  1997年   423篇
  1996年   437篇
  1995年   356篇
  1994年   303篇
  1993年   235篇
  1992年   234篇
  1991年   198篇
  1990年   168篇
  1989年   142篇
  1988年   96篇
  1987年   109篇
  1986年   88篇
  1985年   82篇
  1984年   47篇
  1983年   42篇
  1982年   35篇
  1981年   18篇
  1980年   11篇
  1979年   9篇
  1978年   6篇
  1976年   9篇
  1975年   11篇
  1957年   4篇
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
31.
Alum‐processing is a traditional method to attenuate the toxicity of Pinelliae Rhizoma (tubers of Pinellia ternate, PT). The present study aimed at investigating the chemical and cytotoxic changes during alum processing. Metabolomic profiles of raw and alum‐processed PT were studied based on ultra‐performance liquid chromatography coupled with Orbitrap mass spectrometry. More than 80 chemicals in positive MS mode and 40 chemicals in negative MS mode, such as organic acids, amino acids, glucosides and nucleosides, were identified after multivariate statistical analysis, including principal component analysis and orthogonal partial least‐square discriminant analysis. Almost all of the identified chemical markers were significantly decreased ~10‐ to 100‐fold after alum processing. Meanwhile, the correlations between the chemical markers were assimilated to a positive coefficient from disorderly distribution during the processing. Raw PT extracts could inhibit the proliferation of human carcinoma cells (HCT‐116, HepG2, and A549) at the rate of 40.5, 24.8 and 31.6% more strongly than processed PT. It was concluded that the alum processing of PT could decrease the number of actively water‐soluble principles at the same time as decreasing toxicity. Given the water‐insoluble property of toxic calcium oxalate raphides in PT, we suggest that a more scientific processing method should be sought.  相似文献   
32.
To address the problems associated with poor conductivity and large volume variation in practical applications as a conversion cathode, engineering of hierarchical nanostructured FeOF coupled with conductive decoration is highly desired, yet rarely reported. Herein, 3D starfish-like FeOF on reduced graphene oxide sheets (FeOF/rGO) is successfully prepared, for the first time, through a combination of solvothermal reaction, self-assembly, and thermal reduction. Integrating the structural features of the 3D hierarchical nanostructure, which favorably shorten the path for electron/ion transport and alleviate volumetric changes, with those of graphene wrapping, which can further enhance the electrical conductivity and maintain the structural stability of the electrode, the as-prepared FeOF/rGO composite exhibits a superior lithium-storage performance, including a high reversible capacity (424.5 mA h−1 g−1 at 50 mA g−1), excellent stability (0.016 % capacity decay per cycle during 180 cycles), and remarkable rate capability (275.8 mA h−1 g−1 at 2000 mA g−1).  相似文献   
33.
Han  Jing  Sun  Youhong  Guo  Wei  Deng  Sunhua  Hou  Chuanbin  Qu  Lili  Li  Qiang 《Journal of Thermal Analysis and Calorimetry》2019,135(4):2287-2296
Journal of Thermal Analysis and Calorimetry - In this study, the non-isothermal pyrolysis method was used to investigate the pyrolysis characteristics of oil shale from four areas: namely Nongan,...  相似文献   
34.
Molybdenum carbide (Mo2C) is a promising noble-metal-free electrocatalyst for the hydrogen evolution reaction (HER), due to its structural and electronic merits, such as high conductivity, metallic band states and wide pH applicability. Here, a simple CVD process was developed for synthesis of a Mo2C on carbon cloth (Mo2C@CC) electrode with carbon cloth as carbon source and MoO3 as the Mo precursor. XRD, Raman, XPS and SEM results of Mo2C@CC with different amounts of MoO3 and growth temperatures suggested a two-step synthetic mechanism, and porous Mo2C nanostructures were obtained on carbon cloth with 50 mg MoO3 at 850 °C (Mo2C-850(50)). With the merits of unique porous nanostructures, a low overpotential of 72 mV at current density of 10 mA cm−2 and a small Tafel slope of 52.8 mV dec−1 was achieved for Mo2C-850(50) in 1.0 m KOH. The dual role of carbon cloth as electrode and carbon source resulted into intimate adhesion of Mo2C on carbon cloth, offering fast electron transfer at the interface. Cyclic voltammetry measurements for 5000 cycles revealed that Mo2C@CC had excellent electrochemical stability. This work provides a novel strategy for synthesizing Mo2C and other efficient carbide electrocatalysts for HER and other applications, such as supercapacitors and lithium-ion batteries.  相似文献   
35.
Thermal gas-phase reactions of the ruthenium-oxide clusters [RuOx]+ (x=1–3) with methane and dihydrogen have been explored by using FT-ICR mass spectrometry complemented by high-level quantum chemical calculations. For methane activation, as compared to the previously studied [RuO]+/CH4 couple, the higher oxidized Ru systems give rise to completely different product distributions. [RuO2]+ brings about the generations of [Ru,O,C,H2]+/H2O, [Ru,O,C]+/H2/H2O, and [Ru,O,H2]+/CH2O, whereas [RuO3]+ exhibits a higher selectivity and efficiency in producing formaldehyde and syngas (CO+H2). Regarding the reactions with H2, as compared to CH4, both [RuO]+ and [RuO2]+ react similarly inefficiently with oxygen-atom transfer being the main reaction channel; in contrast, [RuO3]+ is inert toward dihydrogen. Theoretical analysis reveals that the reduction of the metal center drives the overall oxidation of methane, whereas the back-bonding orbital interactions between the cluster ions and dihydrogen control the H−H bond activation. Furthermore, the reactivity patterns of [RuOx]+ (x=1–3) with CH4 and H2 have been compared with the previously reported results of Group 8 analogues [OsOx]+/CH4/H2 (x=1–3) and the [FeO]+/H2 system. The electronic origins for their distinctly different reaction behaviors have been addressed.  相似文献   
36.
Zhu  Hong  Zeng  Xiangbing  Han  Tianli  Li  Xuexue  Zhu  Shuguang  Sun  Bai  Zhou  Ping  Liu  Jinyun 《Journal of Solid State Electrochemistry》2019,23(7):2173-2180
Journal of Solid State Electrochemistry - Since conventional graphite-based anode possesses a low capacity, seeking for high-capacity anode candidates becomes significant for constructing emerging...  相似文献   
37.
The first alkaline-earth metal tin(II) phosphate, BaSn2(PO4)2, has been discovered, which consists of layered structures constructed from strictly alternating [SnO3]4− and [PO4]3− moieties. This compound is expected to have a large birefringence with Δn≈0.071 at 1064 nm, owing to the presence of stereochemically active lone pair metal cations.  相似文献   
38.
The large-scale production of ammonia mainly depends on the Haber–Bosch process, which will lead to the problems of high energy consumption and carbon dioxide emission. Electrochemical nitrogen fixation is considered to be an environmental friendly and sustainable process, but its efficiency largely depends on the activity and stability of the catalyst. Therefore, it is imperative to develop highefficient electrocatalysts in the field of nitrogen reduction reaction (NRR). In this paper, we developed a BiVO4/TiO2 nanotube (BiVO4/TNT) heterojunction composite with rich oxygen vacancies as an electrocatalytic NRR catalyst. The heterojunction interface and oxygen vacancy of BiVO4/TNT can be the active site of N2 dynamic activation and proton transition. The synergistic effect of TiO2 and BiVO4 shortens the proton transport path and reduces the over potential of chemical reaction. BiVO4/TNT has high ammonia yield of 8.54 μg·h−1·cm−2 and high Faraday efficiency of 7.70% in −0.8 V vs. RHE in 0.1 M Na2SO4 solution.  相似文献   
39.
Sun  Qinqin  Wang  Xiuye  Yang  Guolai  Chen  Ye-Hwa  Ma  Fai 《Nonlinear dynamics》2022,109(3):1629-1650
Nonlinear Dynamics - This paper proposes an optimal parameter design of control scheme for mechanical systems by adopting the Stackelberg game theory. The goal of the control is to drive the...  相似文献   
40.
Li  Jun  Zheng  Dayong  Wei  Ning  Sun  Yunfeng  Liu  Li  Yuan  Yuan  Jiang  Qinghua 《Chemistry of Natural Compounds》2022,58(4):650-652
Chemistry of Natural Compounds - A new quassinoid, dehydrobruceantinol B (1), was isolated from the seeds of Brucea javanica, together with two known compounds, bruceantinol (2) and bruceine A (3)....  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