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   4908篇
  免费   196篇
  国内免费   1102篇
化学   4561篇
晶体学   25篇
力学   119篇
综合类   5篇
数学   39篇
物理学   1457篇
  2024年   14篇
  2023年   170篇
  2022年   174篇
  2021年   179篇
  2020年   226篇
  2019年   165篇
  2018年   145篇
  2017年   186篇
  2016年   228篇
  2015年   196篇
  2014年   234篇
  2013年   373篇
  2012年   312篇
  2011年   407篇
  2010年   312篇
  2009年   442篇
  2008年   376篇
  2007年   424篇
  2006年   306篇
  2005年   239篇
  2004年   193篇
  2003年   158篇
  2002年   82篇
  2001年   100篇
  2000年   57篇
  1999年   54篇
  1998年   80篇
  1997年   86篇
  1996年   51篇
  1995年   39篇
  1994年   26篇
  1993年   28篇
  1992年   33篇
  1991年   18篇
  1990年   14篇
  1989年   16篇
  1988年   13篇
  1987年   6篇
  1986年   11篇
  1985年   12篇
  1983年   2篇
  1982年   6篇
  1981年   2篇
  1976年   1篇
  1974年   1篇
  1973年   1篇
  1971年   1篇
  1970年   1篇
  1968年   1篇
  1967年   1篇
排序方式: 共有6206条查询结果,搜索用时 265 毫秒
81.
The replacement of a non-conductive organic binder with a conductive room temperature ionic liquid in fabricating carbon paste electrode has been made. This new electrode due to its enhanced conductivity presented very large current response from electroactive substrates. The novel carbon paste electrode was bulk-modified via the uniform dispersion of Keggin-type phospho polyoxomolybdate (PMo12) in bulky carbons, which possessed excellent electrocatalytic activity for the reduction of nitrite. The pronounced multi-electron catalytic ability was ascribed to the used hydrophobic ionic liquid which constructed an excellent charge-transfer bridge in the bulk of carbon paste electrode, thus facilitated the intake of electrons from reduced PMo12 mediators. In view of their prominent properties, the carbon paste electrode using ionic liquid binder and its bulk-modified electrode take on good prospects of the application in physical chemistry and electroanalytical chemistry fields.  相似文献   
82.
碳糊电极阳极吸附伏安法测定大黄酸   总被引:5,自引:0,他引:5  
在pH4.2的HAc-NaAc底液中,大黄酸在碳糊电极(CPE)上有一灵敏的吸附氧化峰,峰电位为1.14V(vs.SCE)。该氧化峰的二阶导数峰电流与大黄酸的浓度在8.0×10-9~8.0×10-7mol/L(富集120s)范围内呈良好的线性关系(r=0.998),检出限为2×10-9mol/L(S/N=3,富集180s)。探讨了大黄酸在CPE上的伏安性质和电极反应机理,并将本法应用于中药大黄中的大黄酸的测定,结果良好。  相似文献   
83.
利用微波等离子体化学气相沉积法在玻璃孔穴中定位生长纳米碳管电极, 分析了负偏压对纳米碳管电极生长的影响. 该电极对铜离子的电化学检测性能分析结果表明, 所制备的纳米碳管电极具有良好的电化学检测性能, 位于-0.0100 V附近的铜离子的还原峰峰形良好, 其电流在铜离子浓度为0.01~0.30 mmol•L-1时, 与Cu2+浓度呈良好的线性关系, 相关系数为0.9975, 且具有较好的长期稳定性和重现性.  相似文献   
84.
锂离子二次电池碳负极材料的改性   总被引:5,自引:1,他引:5  
吴宇平  万春荣 《电化学》1998,4(3):286-292
作为锂离子二次电池的碳负极材料,其改性方面的研究内容主要有:引入非金属元素,引入金属元素,处理表面及其它方面。纺入的非金属元素有硼,硅,氮,磷和硫。引入的金属元素有钾,铝,镓和钒,镍,钴,铜,铁等过渡金属元素。表面处理的方法包括氧化,形成表面层等。  相似文献   
85.
石墨烯是最近发现的一种具有二维平面结构的碳纳米材料, 它的特殊单原子层结构使其具有许多独特的物理化学性质. 有关石墨烯的基础和应用研究已成为当前的前沿和热点课题之一. 本文仅就目前石墨烯的制备方法、功能化方法以及在化学领域中的应用作一综述, 重点阐述石墨烯应用于化学修饰电极、化学电源、催化剂和药物载体以及气体传感器等方面的研究进展, 并对石墨烯在相关领域的应用前景作了展望.  相似文献   
86.
In the 21st century, hydrogen energy is a novel energy source. Its use is expected to mitigate the problems of environmental pollution and global warming caused by the excessive use of conventional fossil fuels. The hydrogen evolution reaction (HER) for water splitting has attracted considerable attention because of its environmental friendliness. To improve electrocatalyst performance and reduce operation cost, carbon-based metal hybrid materials exhibiting high efficiency and catalytic activity have been developed. Among them, carbon dots (CDs) have garnered significant research attention and have been widely applied in biosensing, bioimaging, and energy conversion/storage because of their facile synthesis, biocompatibility, tunable photoluminescence, excellent stability, and good electronic properties. CDs are widely used as carriers in the construction of electrocatalysts prepared from carbon-based metal hybrid materials. At present, it is believed that CDs exhibit excellent confinement effects, which can effectively inhibit the growth and agglomeration of metal nanoparticles, thereby preparing well-distributed carbon-based metal hybrid materials with a uniform and controllable size. However, the formation process of the small-molecule raw materials of CDs has not been elucidated. In this study, CDs and small-molecule raw materials from synthetic CDs were used as precursors to prepare nitrogen-doped CD-supported ruthenium nanoparticle (Ru@CDs) and small-molecule-supported ruthenium nanoparticle (Ru@Molecule) hybrid materials, respectively. The interaction between the small molecules and Ru in the process of CD formation and the effect on HER performance were explored. Moreover, we prepared different carriers such as metal organic frameworks(MOF), carbon nanotubes (CNTs), and graphene (GO)-supported ruthenium nanoparticle hybrid materials. Among them, Ru@CDs exhibited controllable size and excellent dispersibility and exhibited outstanding HER activity and good stability. Ru@CDs were found to require a low overpotential of 22 mV to reach a current density of 10 mA·cm−2. Moreover, we observed the presence of an intermediate state between the molecules and CDs and demonstrated that the intermediate state exhibits no confinement effect. Furthermore, we found that with increasing calcination temperature, the intermediate state gradually changes to CDs. The unique spatial confinement between CDs and metal ions is key to the formation of monodisperse Ru nanoparticles. Our results confirmed that Ru@CDs serve as excellent HER catalyst supports. This work not only reveals the effect of the unique spatial confinement of CDs on the supported metals and their promoting effect on electrocatalytic activity but also provides guides the future development of CD-based metal hybrid electrocatalysts.  相似文献   
87.
Summary The capabilities of sulfur hexafluoride as a mobile phase for supercritical-fluid chromatography are investigated. An evaluation of its overall utility on the basis of separations of standard aromatic hydrocarbon odel mixtures performed on a variety of bonded-phase, packed columns with UV detection is presented. The dependence of separation performance upon operational parameters is also examined. A comparative evaluation of the chroamtographic properties of supercitrical sulfur hexafluoride and those of supercritical carbon dioxide is developed from these separations under corresponding supercritical state conditions.  相似文献   
88.
Cu/TiO2-NiO上光促表面催化CO2和H2O合成CH3OH反应规律   总被引:8,自引:0,他引:8  
陈崧哲  钟顺和 《物理化学学报》2002,18(12):1099-1103
采用溶胶-凝胶法制备了n(电子型)-p(空穴型) 复合半导体材料0.5%Cu/TiO2-2.0%NiO (w),利用X射线衍射(XRD)、透射电镜(TEM)、红外光谱(IR)、紫外-可见光漫反射(UV-Vis)、程序升温脱附(TPD)技术对材料结构、吸光性能、化学吸附性能进行了表征,研究了该材料对CO2和H2O合成CH3OH的光促表面催化反应(PSSR)规律.结果表明,所制备材料能够明显促进目的反应,室温条件下即有CH3OH生成.在200 ℃下,由于光-表面-热的协同效应,CO2转化率得以提高,且CH3OH的选择性达到87.5% .根据实验结果,得出CO2在材料表面的卧式吸附态为CH3OH的前驱物,并对PSSR机理进行了讨论.  相似文献   
89.
本文研究了一种将电子介体四硫富瓦烯(TTF,Tetrathiafulalene)引入葡萄糖氧化酶微电极的新方法,制成了TTF为介体的碳纤维束葡萄糖氧化酶微电极。该电极制作简单,响应迅速、灵敏,电极寿命可达15天。葡萄糖浓度在1。0×10~(-4)~1.5×10~(-3)mol/L范围内有线性关系。检出限为7×10~(-5)mol/L。用于人体血样中葡萄糖测定获得满意结果。  相似文献   
90.
Microporous carbon membranes were prepared on an -alumina support by a pyrolysis of cationic tertiary amine/anionic polymer composites. The precursor solutions contain a thermosetting resorcinol/formaldehyde (RF) polymer and a cationic tertiary amine. Three types of cationic tertiary amines with different chain lengths were used, such as tetramethlammonium bromide (TMAB), tetrapropylammonium bromide (TPAB) and cetyltrimethylammonium bromide (CTAB). A porous structure was produced by a decomposition of the amine and the resulting pores assisted the further gasification of the RF polymer at high temperature. The carbon/alumina membranes have thin and continuous carbon top layers with a thickness of 1 μm. Gas permeation tests were performed using single gases of CO2, O2, N2, CF4, n-C4H10 and i-C4H10, as well as binary mixtures of CH4/n-C4H10 and N2/CF4 at different temperatures between 23 and 150 °C. The carbon membrane prepared using TMAB showed separation factors higher than 650 for the CH4/n-C4H10 mixtures and higher than 8100 for the N2/CF4 mixture. From the permeation of pure gases with different molecular sizes, the pore sizes of the carbon membrane prepared using TMAB, TPAB and CTAB are estimated to be 4.0, 5.0 and larger than 5.5 Å, respectively, indicating that the micropore size of the carbon membranes is controllable by using different amines.  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