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   10115篇
  免费   1642篇
  国内免费   2310篇
化学   9361篇
晶体学   176篇
力学   191篇
综合类   100篇
数学   30篇
物理学   4209篇
  2024年   8篇
  2023年   114篇
  2022年   215篇
  2021年   296篇
  2020年   384篇
  2019年   367篇
  2018年   348篇
  2017年   370篇
  2016年   462篇
  2015年   454篇
  2014年   569篇
  2013年   1049篇
  2012年   785篇
  2011年   687篇
  2010年   520篇
  2009年   688篇
  2008年   618篇
  2007年   692篇
  2006年   670篇
  2005年   593篇
  2004年   584篇
  2003年   508篇
  2002年   481篇
  2001年   357篇
  2000年   316篇
  1999年   280篇
  1998年   213篇
  1997年   221篇
  1996年   161篇
  1995年   167篇
  1994年   131篇
  1993年   133篇
  1992年   121篇
  1991年   78篇
  1990年   58篇
  1989年   56篇
  1988年   60篇
  1987年   36篇
  1986年   28篇
  1985年   20篇
  1984年   20篇
  1983年   18篇
  1982年   21篇
  1981年   9篇
  1980年   15篇
  1979年   17篇
  1978年   16篇
  1977年   12篇
  1976年   19篇
  1973年   6篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
1.
以有序介孔碳(OMC)球为离子-电子转换层,制备了固态氯离子选择性电极,构建了基于离子敏感的场效应晶体管(ISFET)的手持式传感系统,用于检测人体血清中的氯离子。优化了OMC前驱体的碳化温度,探究了OMC形貌结构对电极传感性能的影响;电极柔性化制备后考察了其在手持系统中对氯离子的检测效果。结果表明,最优条件下,电极在5.12×10^-4~1.02 mol/L的浓度范围呈现线性响应,响应斜率为60 mV/decade。该柔性电极在手持传感系统中展现出高灵敏度和重现性,可用于人体血清样品中氯离子的检测,其回收率为96.3%~104.9%。  相似文献   
2.
In this paper, I study the effect of a small deviation from the Fermi–Dirac statistics on the quantum ion acoustic waves. For this purpose, a quantum hydrodynamic model is developed based on the Polychronakos statistics, which allows for a smooth interpolation between the Fermi and Bose limits, passing through the case of classical particles. The model includes the effect of pressure as well as quantum diffraction effects through the Bohm potential. The equation of state for electrons obeying fractional statistics is obtained and the effect of fractional statistics on the kinetic energy and the coupling parameter is analyzed. Through the model, the effect of fractional statistics on the quantum ion acoustic waves is highlighted, exploring both linear and weakly nonlinear regimes. It is found that fractional statistics enhance the amplitude and diminish the width of the quantum ion acoustic waves. Furthermore, it is shown that a small deviation from the Fermi–Dirac statistics can modify the type structures, from bright to dark soliton. All known results of fully degenerate and non-degenerate cases are reproduced in the proper limits.  相似文献   
3.
This paper describes the processes used at the Fukushima Daiichi plant, Japan, to purify the waste effluents generated in the cooling of damaged reactors. These include primary cesium removal with the Kurion zeolite system and the SARRY system utilizing silicotitanate to remove radiocesium from water recirculated to reactors for cooling. Another process is the ALPS system to purify the retentates of the reverse osmosis plant to further purify the water from radionuclides after primary cesium separation. In ALPS, a major role is played by the transition metal hexacyanoferrate product CsTreat and sodium titanate SrTreat in the removal of radiocesium and radiostrontium, respectively. The performance of these four exchangers (zeolite, silicotitanate, hexacyanoferrate, and sodium titanate) is critically analyzed with respect to processing capacities and the decontamination factors obtained in the processes. Furthermore, general information on preparation, structure and ion exchange of these ion-exchanger categories is given with additional information on their use in nuclear waste effluent treatment processes. Finally, the importance of selectivity and associated factors are discussed.  相似文献   
4.
Metal oxides have a large storage capacity when employed as anode materials for lithium‐ion batteries (LIBs). However, they often suffer from poor capacity retention due to their low electrical conductivity and huge volume variation during the charge–discharge process. To overcome these limitations, fabrication of metal oxides/carbon hybrids with hollow structures can be expected to further improve their electrochemical properties. Herein, ZnO‐Co3O4 nanocomposites embedded in N‐doped carbon (ZnO‐Co3O4@N‐C) nanocages with hollow dodecahedral shapes have been prepared successfully by the simple carbonizing and oxidizing of metal–organic frameworks (MOFs). Benefiting from the advantages of the structural features, i.e. the conductive N‐doped carbon coating, the porous structure of the nanocages and the synergistic effects of different components, the as‐prepared ZnO‐Co3O4@N‐C not only avoids particle aggregation and nanostructure cracking but also facilitates the transport of ions and electrons. As a result, the resultant ZnO‐Co3O4@N‐C shows a discharge capacity of 2373 mAh g?1 at the first cycle and exhibits a retention capacity of 1305 mAh g?1 even after 300 cycles at 0.1 A g?1. In addition, a reversible capacity of 948 mAh g?1 is obtained at a current density of 2 A g?1, which delivers an excellent high‐rate cycle ability.  相似文献   
5.
A new approach for the synthesis of functionalized racemic 3,4-dihydroferroceno[c]pyridines via the Ritter reaction of 2-methyl-1-ferrocenylpropan-1-ol with nitriles in the presence of methansulfonic acid was developed. The scope and limitations of the reaction were evaluated. Selected racemic 3,4-dihydroferroceno[c]pyridines were successfully separated by preparative HPLC on a Chiralcel OD-H column. The absolute configuration of the enantiomers was determined by X-ray crystal structure analysis.  相似文献   
6.
The aqueous solution chemistry of niobium is underexplored, and well characterized aqua complexes are scarce. In this contribution, a new niobium aqua complex was obtained by treatment of Zn‐reduced ethanolic solution of NbCl5 with HCl in the presence of a selenide source (ZnSe). This is the first example of selenium containing aqua complex of niobium. The yellow‐green aqua complex was isolated by cation‐exchange chromatography and transformed into corresponding isothiocyanate complex by ligand exchange, which was crystallized as (PyH)4.5[H1.5Nb4SeO5(NCS)10] · 0.5H2O. X‐ray structural analysis revealed a metal‐metal bonded tetranuclear {Nb44‐Se)(μ2‐O)5}4+ core with a capping μ4‐Se ligand.  相似文献   
7.
2D MoS2 has a significant capacity decay due to the stack of layers during the charge/discharge process, which has seriously restricted its practical application in lithium‐ion batteries. Herein, a simple preform‐in situ process to fabricate vertically grown MoS2 nanosheets with 8–12 layers anchored on reduced graphene oxide (rGO) flexible supports is presented. As an anode in MoS2/rGO//Li half‐cell, the MoS2/rGO electrode shows a high initial coulomb efficiency (84.1%) and excellent capacity retention (84.7% after 100 cycles) at a current density of 100 mA g?1. Moreover, the MoS2/rGO electrode keeps capacity as high as 786 mAh g?1 after 1000 cycles with minimum degradation of 54 µAh g?1 cycle?1 after being further tested at a high current density of 1000 mA g?1. When evaluated in a MoS2/rGO//LiCoO2 full‐cell, it delivers an initial charge capacity of 153 mAh g?1 at a current density of 100 mA g?1 and achieves an energy density of 208 Wh kg?1 under the power density of 220 W kg?1.  相似文献   
8.
In recent years, hydrophobic deep eutectic solvents as new generation of green solvents have attracted wide attention in liquid microextraction technique. In this article, four hydrophobic deep eutectic solvents composed of trioctylmethylammonium chloride and oleic acid were designed and prepared firstly. Combined with high‐performance liquid chromatography, these deep eutectic solvents were used as an extraction solvent in vortex‐assisted dispersive liquid–liquid microextraction for the selective enrichment and indirect determination of trace nitrite from real water and biological samples. This method is based on the diazotization‐coupling reaction of nitrite with p‐nitroaniline and diphenylamine in acidic water, and then the nitrite is quantified indirectly by measuring the obtained azo compounds. Some factors influencing the extraction efficiency, including the reaction and extraction conditions, were investigated. Under the optimized conditions, the method has a linear range of 1–300 μg/L with a correlation coefficient of 0.9924, limit of detection of 0.2 μg/L, limit of quantitation of 1 μg/L, intraday and interday relative standard deviations of 4.0 and 6.0%. This method was successfully applied in determination of nitrite from three environmental water and two biological samples with the recovery in the range of 90.5–115.2%. In addition, these results were well agreement with those obtained by the conventional Griess method.  相似文献   
9.
This study describes the development of an analytical methodology based on the use of microchip electrophoresis (ME) devices integrated with capacitively coupled contactless conductivity detection (C4D) for the separation and detection of inorganic anions in post‐blast explosive residues. The best separation condition was achieved using a running buffer composed of 35 mmol/L lactic acid, 10 mmol/L histidine and 0.070 mmol/L cetyl(trimethyl ammonium) bromide. For C4D measurements, the highest sensitivity was obtained applying a 700 kHz sinusoidal wave with excitation voltage of 20 Vpp. The separation of Cl?, NO3?, NO2?, SO42?, ClO4? and ClO3? was performed within ca. 150 s with baseline resolution and efficiencies between 4.4 × 104 and 1.7 × 105 plates/m. The found limits of detection ranged between 2.5 and 9.5 μmol/L. Last, real samples of post‐blast explosive residues were analyzed on the ME‐C4D devices obtaining successfully the determination of Cl?, NO3? and SO42?. The achieved concentration values varied between 12.8–72.5 mg/L for Cl?, 1.7–293.1 mg/L for NO3? and 1.3–201.3 mg/L for SO42?. The data obtained using ME‐C4D devices were in good agreement with the concentrations found by ion chromatography. The approach reported herein has provided short analysis time, instrumental simplicity, good analytical performance and low cost. Furthermore, the ME‐C4D devices emerge as a powerful and portable analytical platform for on‐site analysis demonstrating to be a promising tool for the crime scene investigation.  相似文献   
10.
制备了一种可定性定量检测水溶液中三价铁离子的含铕聚苯乙烯微球, 分别用固体核磁碳谱(13C CP/MAS NMR)、 傅里叶变换红外光谱(FTIR)、 X射线光电子能谱(XPS)、 扫描电子显微镜(SEM)、 透射电子显微镜(TEM)、 元素分析、 粒度分析和ζ电位分析等对其化学组成和结构形貌进行表征. 当铕配合物单体用量低于2.5%时, 可以得到稳定的单分散键合型含铕聚苯乙烯微球. 用紫外光激发时, 该含铕聚苯乙烯微球发射铕离子的特征红光. Fe3+能猝灭该微球的荧光, 酸根离子和其它金属离子对其干扰较少; 猝灭效率与Fe3+浓度在0~300 μmol/L浓度范围内均呈线性关系; 随着铕配合物单体用量的增加, 微球的荧光增强, 其在检测Fe3+的荧光时, 猝灭常数(KSV)增加, 检测限(LOD)下降. 调节铕配合物单体的用量, 可获得热性能优异、 红光发射强度高且稳定性好的单分散聚苯乙烯荧光微球, 对Fe3+荧光检测显示出较高的选择性, 在生物检测和环境保护等领域具有较高的应用价值.  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