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   7191篇
  免费   646篇
  国内免费   892篇
化学   4987篇
晶体学   62篇
力学   1178篇
综合类   53篇
数学   615篇
物理学   1834篇
  2024年   5篇
  2023年   177篇
  2022年   220篇
  2021年   300篇
  2020年   342篇
  2019年   221篇
  2018年   200篇
  2017年   265篇
  2016年   352篇
  2015年   288篇
  2014年   384篇
  2013年   442篇
  2012年   483篇
  2011年   475篇
  2010年   410篇
  2009年   494篇
  2008年   430篇
  2007年   420篇
  2006年   396篇
  2005年   356篇
  2004年   320篇
  2003年   264篇
  2002年   178篇
  2001年   176篇
  2000年   143篇
  1999年   121篇
  1998年   121篇
  1997年   117篇
  1996年   73篇
  1995年   89篇
  1994年   66篇
  1993年   75篇
  1992年   58篇
  1991年   43篇
  1990年   43篇
  1989年   30篇
  1988年   34篇
  1987年   24篇
  1986年   11篇
  1985年   18篇
  1984年   13篇
  1983年   7篇
  1982年   14篇
  1981年   3篇
  1980年   3篇
  1979年   7篇
  1978年   3篇
  1971年   4篇
  1969年   1篇
  1957年   6篇
排序方式: 共有8729条查询结果,搜索用时 15 毫秒
131.
We report on the synthesis and electrochemical characterization of nanohybrid polypyrrole (PPy) (PPy/Fe2O3) materials for electrochemical storage applications. We have shown that the incorporation of nanoparticles inside the PPy notably increases the charge storage capability in comparison to the “pure” conducting polymer. Incorporation of large anions, i.e., paratoluenesulfonate, allows a further improvement in the capacity. These charge storage modifications have been attributed to the morphology of the composite in which the particle sizes and the specific surface area are modified with the incorporation of nanoparticles. High capacity and stability have been obtained in PC/NEt4BF4 (at 20 mV/s), i.e., 47 mAh/g, with only a 3% charge loss after one thousand cyles. The kinetics of charge–discharge is also improved by the hybrid nanocomposite morphology modifications, which increase the rate of insertion–expulsion of counter anions in the bulk of the film. A room temperature ionic liquid such as imidazolium trifluoromethanesulfonimide seems to be a promising electrolyte because it further increases the capacity up to 53 mAh/g with a high stability during charge–discharge processes.  相似文献   
132.
《中国化学快报》2021,32(10):3221-3225
Electrochemical heterogeneous catalytic ozonation (E-catazone) is a promising and advanced oxidation technology that uses a titanium dioxide nanoflower (TiO2-NF)-coated porous Ti gas diffuser as an anode material. Our previous study has highlighted that the importance of the TiO2-NF coating layer in enhancing OH production and rapidly degrading O3-resistant drugs. It is well known that the properties of TiO2-NF are closely related to its sintering temperature. However, to date, related research has not been conducted in E-catazone systems. Thus, this study evaluated the effect of the sintering temperature on the degradation of the O3-resistant drug para-chlorobenzoic acid (p-CBA) using both experimental and kinetic modeling and revealed its influence mechanism. The results indicated that the TiO2-NF sintering temperature could influence p-CBA degradation and OH production. TiO2-NF prepared at 450 °C showcased the highest p-CBA removal efficiency (98.5% in 5 min) at a rate of 0.82 min−1, and an OH exposure of 8.41 × 10−10 mol L−1 s. Kinetic modeling results and interface characterization data revealed that the sintering temperature could alter the TiO2 crystallized phase and the content of surface-adsorbed oxygen, thus affecting the two key limiting reactions in the E-catazone process. That is, ≡TiO2 surface reacted with H2O to form TiO2-(OH)2, which then heterogeneously catalyzed O3 to form OH. Consequently, E-catazone with a TiO2-NF anode prepared at 450 °C generated the highest surface reaction rate (5.00 × 10−1 s−1 and 4.00 × 10-3 L mol-1 s−1, respectively), owing to its higher anatase content and adsorbed oxygen. Thus, a rapid O3-TiO2 reaction was achieved, resulting in an enhanced OH formation and a highly effective p-CBA degradation. Overall, this study provides novel baseline data to improve the application of E-catazone technology.  相似文献   
133.
分子印迹电化学传感器的研究进展   总被引:1,自引:0,他引:1  
本文综述了分子印迹电化学传感器的制备及其在电分析化学领域中的应用研究。引用文献83篇。  相似文献   
134.
Heteroleptic nickel(II) complexes [NiL2L′] of a series of monoanionic and potentially bidentate N‐2‐pyridyl‐sulfonamide ligands [HL] and 2,2′‐bipyridine or 1,10‐Phenanthroline (L′) have been prepared by electrochemical oxidation of a nickel anode in an acetonitrile solution of the ligands. The complexes have been characterized by microanalysis, IR and electronic spectroscopy, magnetic measurements and LSI mass spectrometry. The crystal structure of [Ni(Ms6mepy)2(bipy)] has been determined by x‐ray diffraction and shows the metal in an octahedral NiN6 environment. Octahedral structures are also proposed for the other complexes with the N‐2‐pyridyl‐sulfonamide ligands acting as N,N′ or N, O bidentate systems, depending on the position of the methyl substituent on the pyridine ring.  相似文献   
135.
The novel applications of molybdenum disulfide in recent research were reviewed, such as in lubricant, catalyst and photoelectrochemical solar cells. Recently, we found that LiMoS2 is a good candidate for new anode materials for lithium ion batteries with high lithium storage capacity.Here, the anode material LiMoS2 was synthesized by a hydrothermal method at 150℃ and the electrochemical characterization as an anode material for lithium ion batteries was examined.put in Teflon-lined stainless steel autoclaves of capacity 40 mL. Distilled water was used to fill the autoclaves to 70 % of the total volume. The autoclaves were maintained at 150℃ for 24 h and then cooled naturally. The resulting dark-gray powders were filled and washed with distilled water,diluted hydrochloric acid and ethanol, successively. The final products were dried at 80℃ for 24 h.The powder X-ray diffraction pattern showed the prepared LiMoS2 was amorphous structure. A test cell using LiMoS2 as the active material was discharged and charged between 3 and 0.01 V with respect to Li metal at a constant current density of C/5 (that is, one lithium per formula unit in 5 hours). During the first discharge, the potential rapidly drops to reach a large plateau at 2.2 V, then slowly drops to the other plateau at 0.8 V, and then continuously decreases down to 0.01V. There is only a plateau at 1.35 V in the subsequent discharge curves. The plateaus of charge potential appear at about 1.9 V.The irreversible loss was 41% in the first cycle. The ratio of discharge and charge is more than 99%in the subsequent cycles. Moreover, the ratio of discharge and charge almost reaches 100% after thedemonstrated that LiMoS2 has a very high capacity and a good cycle-ability as an anode material forlithium ion batteries.  相似文献   
136.
The corrosion and passivation of Zn powder particles dispersed in a paste electrode immersed in 0.5 M Na2SO4 and 5×10–3 M Na2HPO4 solutions were studied mainly by electrochemical impedance spectroscopy. The role played by diffusion in the mechanism of anodic oxidation of zinc powder particles has been shown. It was demonstrated that the anodic reactionof Zn powder in neutral or near neutral media involves at least two adsorbed intermediates. By simulating the porous structure of the electrode, some information about porous nature of zinc electrode could be extracted. Electronic Publication  相似文献   
137.
[Co(H2o)4(NCS)2](18—C—6)的薄层光谱电化学研究   总被引:2,自引:0,他引:2  
利用光谱电化学方法来研究冠醚类化合物的文章尚未见报导.本文在测定用凝胶法合成的[Co(H_2O)(NCS)_2](18-C-6)的核磁共振谱和红外光谱的基础上,使用循环伏安法和薄层光谱电化学技术,在金微栅电极上测定了此配合物在乙腈溶剂中的第一步克式量电势(E~0′)和电子转移数(n),并推测了电还原反应机理.  相似文献   
138.
The present short review deals with electroanalytical aspects of electrochemical response of ascorbic acid (Vitamin C) at conducting and electrogenerated polymer modified electrodes. Two main topics are considered: (i) electrocatalytic oxidation of ascorbate at conducting polymer modified electrodes, leading to electroanalytical techniques for ascorbate assay, and (ii) retardation of ascorbate penetration through a layer of electrogenerated polymers, leading to permselective coatings and their diverse uses, especially for biosensing devices.  相似文献   
139.
《Electroanalysis》2004,16(12):1051-1058
The voltammetric behavior of α‐ketoglutarate (α‐KG) at the hanging mercury drop electrode (HMDE) has been investigated in acetate buffer solution. Under the optimum experimental conditions (pH 4.5, 0.2 M NaAc‐HAc buffer solution), a sensitive reductive wave of α‐KG was obtained by linear scan voltammetry (LSV) and the peak potential was ?1.18 V (vs. SCE), which was an irreversible adsorption wave. The kinetic parameters of the electrode process were α=0.3 and ks=0.72 1/s. There was a linear relationship between peak current ip, α‐KG and α‐KG concentration in the range of 2×10?6–8×10?4 M α‐KG. The detection limit was 8×10?7 M and the relative standard deviation was 2.0% (Cα‐KG=8×10?4 M, n=10). Applications of the reductive wave of α‐KG for practical analysis were addressed as follows: (1) It can be used for the quantitative analysis of α‐KG in biological samples and the results agree well with those obtained from the established ultraviolet spectrophotometric method. (2) Utilizing the complexing effect between α‐KG and aluminum, a linear relationship holds between the decrease of peak current of α‐KG Δip and the added Al concentration Cequation/tex2gif-inf-5.gif in the range of 5.0×10?6–2.5×10?4 M. The detection limit was 2.2×10?6 M and the relative standard deviation was 3.1% (Cequation/tex2gif-inf-6.gif=4×10?5 M, n=10). It was successfully applied to the detection of aluminum in water and synthetic biological samples with satisfactory results, which were consistent with those of ICP‐AES. (3) It was also applied to study the effect of AlIII on the glutamate dehydrogenase (GDH) activity in the catalytically reaction of α‐KG+NH +NADH?L ‐glutamate+NAD++H2O by differential pulse polarography (DPP) technique. By monitoring DPP reductive currents of NAD+ and α‐KG, an elementary important result was found that Al could greatly affect the activity of GDH. This study could be attributed to intrinsic understanding of the aluminum's toxicity in enzyme reaction processes.  相似文献   
140.
生物样品中神经递质含量的测定   总被引:5,自引:0,他引:5  
用反相高效液相色谱 -电化学检测法 ,同时测定了小鼠脑组织以及人血清中的 6种神经递质的含量。以柠檬酸钠缓冲溶液和甲醇作流动相 ,优化后得到最佳色谱条件。在 1~ 2 0 0× 1 0 - 3mg/ L范围内 ,浓度与响应的线性关系良好 ,各待测物的检出限可达 0 .4~ 5.0× 1 0 - 3mg/ L。  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