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   2839篇
  免费   293篇
  国内免费   266篇
化学   2171篇
晶体学   34篇
力学   133篇
综合类   28篇
数学   251篇
物理学   781篇
  2024年   12篇
  2023年   72篇
  2022年   127篇
  2021年   118篇
  2020年   116篇
  2019年   139篇
  2018年   103篇
  2017年   69篇
  2016年   118篇
  2015年   116篇
  2014年   144篇
  2013年   178篇
  2012年   216篇
  2011年   233篇
  2010年   148篇
  2009年   131篇
  2008年   160篇
  2007年   165篇
  2006年   136篇
  2005年   137篇
  2004年   83篇
  2003年   63篇
  2002年   83篇
  2001年   50篇
  2000年   42篇
  1999年   36篇
  1998年   36篇
  1997年   33篇
  1996年   36篇
  1995年   35篇
  1994年   25篇
  1993年   25篇
  1992年   34篇
  1991年   13篇
  1990年   28篇
  1989年   18篇
  1988年   15篇
  1987年   15篇
  1986年   11篇
  1985年   13篇
  1984年   14篇
  1983年   9篇
  1982年   6篇
  1981年   7篇
  1980年   4篇
  1979年   5篇
  1978年   4篇
  1975年   3篇
  1971年   2篇
  1959年   4篇
排序方式: 共有3398条查询结果,搜索用时 15 毫秒
831.
A rapid, simple miniaturised photometrical method was developed for the determination of nitrate and/or nitrite in freshwater samples. All procedures, including sample buffering, reduction by copperised cadmium granules, colour development and absorbance determination, were completed in a 96-well microplate. The factors governing the nitrate reduction and its recovery were investigated in detail, and the optimised analysing conditions were established. Nitrate was quantitatively reduced by copperised cadmium granules with a high reduction efficiency (96.59 ± 0.96%). The proposed method gave a linear calibration ranging from 0.01 to 1.50 mg L−1 for NO2-N and 0.02 to 1.50 mg L−1 for NO3-N. The detection limits for nitrite and nitrate were 2 and 4 μg L−1, respectively. The proposed method allowed at least 48 samples to be simultaneously analysed in duplicate, with good precision, within 90 min for nitrate and 30 min for nitrite, and was successfully applied to actual freshwater sample analysis with a recovery of 98.02 ± 1.04% for nitrite and 99.72 ± 1.39% for nitrate. This method produced accurate results comparable to standard methods, provided a much higher sample throughput than conventional methods and could be routinely used in actual freshwater sample monitoring.  相似文献   
832.
The FeCl3-catalyzed aerobic oxidation process for the synthesis of benzoxazoles, benzothiazole and benzimidazole has been discovered. This method has proved to be effective to a wide range of substrates, and it has been applied for the synthesis of JTP-426467.  相似文献   
833.
One of the main challenges in deep-water drilling is gas-hydrate plugs, which make the drilling unsafe. Some oil-based drilling fluids (OBDF) that would be used for deep-water drilling in the South China Sea were tested to investigate the characteristics of gas-hydrate formation, agglomeration and inhibition by an experimental system under the temperature of 4 ℃ and pressure of 20 MPa, which would be similar to the case of 2000 m water depth. The results validate the hydrate shell formation model and show that the water cut can greatly influence hydrate formation and agglomeration behaviors in the OBDF. The oleophobic effect enhanced by hydrate shell formation which weakens or destroys the interfacial films effect and the hydrophilic effect are the dominant agglomeration mechanism of hydrate particles. The formation of gas hydrates in OBDF is easier and quicker than in water-based drilling fluids in deep-water conditions of low temperature and high pressure because the former is a W/O dispersive emulsion which means much more gas-water interfaces and nucleation sites than the later. Higher ethylene glycol concentrations can inhibit the formation of gas hydrates and to some extent also act as an anti-agglomerant to inhibit hydrates agglomeration in the OBDF.  相似文献   
834.
In this paper, we have developed a solution-phase template approach to synthesize Cu(2)S nanoribbons for the first time. Bi(2)S(3) nanoribbons act as both template and reactant when treated with small CuCl particles, generating Cu(2)S nanoribbons with the assistance of the solvent ethanol. Nanoribbons with different compositions of Bi(2)S(3) and Cu(2)S also could be obtained through controlling the reaction time. This kind of template method is expected to be a general template approach due to its slow reaction rate and simplicity.  相似文献   
835.
The NO reduction features over a noble-metal-free NO(x) storage/reduction catalyst ([Ca24Al28O64](4+*)4O-/K, defined as C12A7-O-/K), including the NO conversion, the N2 selectivity, and sulfur tolerance, were investigated with hydrogen and C3H6 as the reducing agents in a fixed-bed continuous flow reactor. The NO conversion and the N2 selectivity on the C12A7-O-/K catalyst mainly depends on the sample temperature, the percentage of potassium, the reducing agents, and the composition of the mixture of gases. The C12A7-O-/10%K catalyst possessed the highest selective reduction ability (to N2) among the catalysts C12A7-O-/x%K. Over 50% of NO can be reduced to N2 with H2 as the reduction agent at 550-700 degrees C. The C12A7-O-/K catalyst also shows higher NO(x) storage capacity (183.9 micromol/g at about 550 degrees C) as well as sulfur tolerance for both the NO(x) storage and the reduction processes. The catalyst characteristics and the intermediate species formed in the NO storage and reduction processes were investigated by the X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and time-of-flight mass spectrometry. The mechanism of NO(x) reduction was addressed according to the above investigations.  相似文献   
836.
等离激元效应在光催化体系中的集成为实现广谱光吸收提供了一个新的途径,然而等离激元热电子的较低迁移率和不确定扩散方向使得其光催化效率仍较低.等离激元金属与n型半导体接触后,其界面间会形成肖特基结.在特定波长太阳光照射下,等离激元金属将其表面等离子体能量聚集在表面自由电子上,进而产生热电子.当这些热电子具有的能量高于肖特基势垒时,热电子便可注入到半导体导带上.与此同时,半导体上的电子可以通过肖特基接触发生回流,与金属上的空穴复合,进而降低半导体-等离激元金属复合材料的光催化性能.因此,为了提高光催化效率,如何调控等离激元热电子迁移和充分利用等离激元效应是一个重要挑战.本文尝试将"表面异质结"与肖特基结相结合的复合结构,得以有效地调控等离激元热电子的迁移.在该复合结构中,金纳米颗粒和铂纳米颗粒分别作为等离激元吸光单元和助催化剂,集成在TiO_2纳米片表面.其中"表面异质结"是由TiO_2纳米片的两种不同表面晶面所构成,我们选择由{001}和{101}两组晶面组成的TiO_2纳米片作为半导体衬底.该结构中的{001}晶面导带能级高于{101}导带能级,因而电子由高能级的{001}流向低能级的{101}晶面,可以用来引导等离激元热电子从可见光响应的金纳米颗粒向TiO_2进行高效转移.通过巯基丙酸的桥联作用,将等离激元Au纳米颗粒锚定在TiO_2纳米片的{001}晶面上,获得Au-TiO_2{001}样品.另一方面,利用TiO_2纳米片自身光生电荷导向性光沉积,得到与{101}晶面结合形成的Au-TiO_2{101}样品.我们对两组样品进行光电流和光催化产氢实验对比,确认在"表面异质结"诱导下Au-TiO_2{001}样品中Au产生的光生热电子可以更好地注入到TiO_2纳米片导带上.我们进一步通过光沉积Pt纳米颗粒来判定光生电子所能到达的区域,验证了以上结论.与此同时,肖特基结由铂纳米颗粒与TiO_2纳米片所形成,可以促使电子由TiO_2向铂纳米颗粒进行转移,而避免发生向金纳米颗粒的反向迁移,从而在Au-TiO_2体系中实现高效的单向载流子转移.基于该设计,等离激元光催化剂实现了明显改善的全谱光催化产氢性能.本文为全谱光催化的复合结构理性设计提供了一个新的思路.  相似文献   
837.
Over the past two decades, supramolecular gels have attracted significant attention from scientists in diverse research fields and have been extensively developed. This review mainly focuses on the significant achievements in supramolecular gels and catalysis. First, by incorporating diverse catalytic sites and active organic functional groups into gelator molecules, supramolecular gels have been considered as a novel matrix for catalysis. In addition, these rationally designed supramolecular gels also provide a variety of templates to access metal nanocomposites, which may function as catalysts and exhibit high activity in diverse catalytic transformations. Finally, as a new kind of biomaterial, supramolecular gels formed in situ by self‐assembly triggered by catalytic transformations are also covered herein.  相似文献   
838.
Summary Results for up to 12 trace elements in some newer biological materials of the NBS Washington (Citrus Leaves, New Bovine Liver, Wheat and Rice Flours, Milk Powder, Stabilized Wine) are reported using radiochemical neutron activation analysis. A discussion of the techniques and problems of standardization and the correct use of standards is included.
Radiochemische Neutronen-Aktivierungs-Analyse zur Standardisierung von Spurenelementen in biologischen Referenzproben in ng-Mengen
Zusammenfassung Ergebnisse für bis zu 12 Spurenelemente in einigen neuen biologischen Proben des NBS, Washington, (Citrus-Laub, frische Rindsleber, Weizenund Reismehl, Milchpulver, Wein) wurden mitgeteilt, die mittels radiochemischer Neutronen-Aktivierungs-Analyse erhalten wurden. Eine Diskussion der Verfahren, der Probleme der Standardisierung sowie der korrekten Verwendung der Standardproben wurde geboten.


Presented in part at the 9th International Symposium on Microchemical Techniques, Amsterdam, August 1983.  相似文献   
839.
We present the phase behavior and thermodynamics of the catanionic mixture of the gemini surfactant hexanediyl-alpha,omega-bis(dodecyldimethylammonium bromide), designated here as 12-6-12Br(2), and sodium dodecyl sulfate (SDS) over the full range of composition, at the water-rich corner. Visual and turbidity measurements of the mixtures provide some basic macroscopic information on phase behavior. The structure of the aggregates formed spontaneously in the mixtures has been observed with TEM. As the molar fraction of SDS, X(SDS), is increased, at constant total surfactant concentration, the aggregation morphologies change gradually from gemini-rich micelles, through multiphase regions containing a precipitate (catanionic surfactant) and a vesicle region, to SDS-rich micelles. From isothermal titration calorimetry measurements, the phase boundaries and corresponding enthalpy changes for phase transitions have been obtained. The formation of the different microstructures, in particular, the spontaneously formed vesicles in the SDS-rich side, is discussed on the basis of geometric and electrostatic effects occurring in the SDS-gemini mixture.  相似文献   
840.
This Letter describes the first synthesis of fivefold twinned nanorods and right bipyramids of palladium in an aqueous solution, with ascorbic acid as a reducing agent and in the presence of bromide. Like the silver system, these two types of nanostructures are derived from multiple and single twinned seeds, respectively. The ascorbic acid, bromide, and reaction temperature all play important roles in the synthesis.  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