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   916篇
  免费   28篇
  国内免费   240篇
化学   970篇
力学   29篇
综合类   1篇
数学   27篇
物理学   157篇
  2023年   74篇
  2022年   23篇
  2021年   29篇
  2020年   33篇
  2019年   30篇
  2018年   21篇
  2017年   26篇
  2016年   20篇
  2015年   26篇
  2014年   29篇
  2013年   70篇
  2012年   45篇
  2011年   56篇
  2010年   38篇
  2009年   50篇
  2008年   60篇
  2007年   70篇
  2006年   58篇
  2005年   62篇
  2004年   48篇
  2003年   33篇
  2002年   32篇
  2001年   25篇
  2000年   38篇
  1999年   22篇
  1998年   11篇
  1997年   15篇
  1996年   18篇
  1995年   17篇
  1994年   14篇
  1993年   12篇
  1992年   10篇
  1991年   20篇
  1990年   8篇
  1989年   9篇
  1988年   14篇
  1987年   4篇
  1986年   3篇
  1985年   1篇
  1984年   2篇
  1982年   2篇
  1981年   1篇
  1980年   4篇
  1979年   1篇
排序方式: 共有1184条查询结果,搜索用时 15 毫秒
71.
Gold nanoparticles have been employed in biomedicine since the last decade because of their unique optical, electrical and photothermal properties. Present review discusses the microbial synthesis, properties and biomedical applications of gold nanoparticles. Different microbial synthesis strategies used so far for obtaining better yield and stability have been described. It also includes different methods used for the characterization and analysis of gold nanoparticles, viz. UV–visible spectroscopy, Fourier transform infrared spectroscopy, X ray diffraction spectroscopy, scanning electron microscopy, ransmission electron microscopy, atomic force microscopy, electron dispersive X ray, X ray photoelectron spectroscopy and cyclic voltametry. The different mechanisms involved in microbial synthesis of gold nanoparticles have been discussed. The information related to applications of microbially synthesized gold nanoparticles and patents on microbial synthesis of gold nanoparticles has been summarized.  相似文献   
72.
葛明 《催化学报》2014,35(8):1410-1417
采用简易离子交换法制备可见光驱动Ag3PO4光催化剂.通过X射线衍射、场发射扫描电子显微镜、N2吸附-脱附、紫外-可见漫反射光谱及傅里叶变换红外光谱对所制备的Ag3PO4催化剂进行表征.结果表明,在可见光照射下,Ag3PO4催化剂对罗丹明B降解表现出优越的光催化活性,但对甲基橙的降解活性低,这归因于Ag3PO4催化剂对甲基橙分子吸附量低.可见光照Ag3PO4反应体系中,空穴和超氧自由基共同发挥作用导致罗丹明B和甲基橙光催化降解.在罗丹明B的协助作用下,Ag3PO4催化剂对甲基橙的可见光催化降解活性大大增强,这是由于罗丹明B的存在可产生更多的超氧自由基,从而使甲基橙进一步降解.  相似文献   
73.
采用原位红外光谱研究了在具有短程有序Ce-O-Ti结构的非晶Ce-Ti氧化物上NH3选择性催化还原(SCR) NOx反应. 在反应条件下,催化剂表面主要被NH3吸附物种覆盖,而检测不到NOx吸附物种. 经测定,NO的反应级数为0.5-0.6,表明Langmuir-Hinshelwood机理和Eley-Rideal机理同时存在. 可能的机理是NH3吸附物种和弱吸附的NOx反应,生成NHyNO3 (y = 0-4)活性中间物种,并通过GAUSSIAN计算和原位红外结果证实了它们的存在. Ce-O-Ti结构中Ce与Ti之间表现出原子尺度的相互作用,所以在SCR反应的活性温度窗口下,催化剂的氧化还原活性提高.  相似文献   
74.
The present study comparatively investigated the ultrasonic degradation of ketoprofen (KET) and paracetamol (PCT) in water. Ultrasonic irradiation at 555 kHz achieved rapid degradation of KET and PCT in water, the removal efficiencies of KET (2.5–80 μM) and PCT (2.5–80 μM) reached 87.7%-100% and 50.6%-86.9%, respectively, after 10 min of reaction under an ultrasonic power of 60 W. The degradation behaviors of both KET and PCT followed the Langmuir-Hinshelwood model. KET was eliminated faster than PCT because of its higher hydrophobicity. Acidic media favored ultrasonic degradation of KET and PCT. Organic compounds in water matrices exerted a great negative effect on the ultrasonic degradation rates of KET and PCT major by competing with target compounds with the generated radicals at the bubble/water interfacial region. The effects of anions were species dependent. The introduction of ClO4 and Cl enhanced KET and PCT degradation to different extents, while the introduction of HCO3 posed a negative effect on both KET and PCT. KET and PCT degradation are accompanied by the generation of several transform intermediates, as identified via LC/MS/MS analysis, and corresponding reaction pathways have been proposed. A human umbilical vein endothelial cell (HUVEC) toxicity evaluation indicated that ultrasonic treatment was capable of controlling the toxicity of KET or PCT degradation. Of note, the enhanced formation of disinfection byproducts (DBPs), i.e., trichloromethane (TCM) and trichloronitromethane (TCNM), was found due to chlorination after ultrasonic treatment for both KET and PCT.  相似文献   
75.
Gas-phase pyrolysis (static and FVP) of 1-aroylbenzotriazoles gave the corresponding substituted benzoxazole, benzimidazole, benzamide, N-phenylbenzamide, phenanthridin-6(5H)-one derivatives and 1-cyanocyclopentadiene. The present kinetic and mechanistic findings also provide further evidence of the involvement of biradical or carbene reactive intermediates in the reaction pathway of gas-phase pyrolysis of benzotriazoles.  相似文献   
76.
The ethylene polymerization reaction of a neutral nickel catalyst was studied by DFT calculations at the Becke3LYP/6-31G(d) level of theory. As in related cases a β-agostic bond stabilizes the nickel alkyl ground states. Transition states for the insertion of the olefin show a distinct α-agostic interaction, which has not been observed for late metal polymerization catalysts before. An ethylene-alkyl complex was identified as the resting state of the reaction. The overall barrier height of the reaction amounts to 17.54 kcal/mol, which slightly increases to 17.60 kcal/mol for the polymerization of deuterated ethylene. Therefore, a small positive kinetic isotope effect (kH/kD = 1.09) can be calculated, which is caused by the α-agostic interaction in the transition state. A comparison to other late metal based polymerization systems reveals that the ethylene coordination step of highly active catalysts is significantly lower in energy compared to catalysts which are only moderately active.  相似文献   
77.
在室温下通过氧化还原反应制备了AgCuSe三元纳米棒.用X射线粉末衍射、透射电镜和X射线光电子能谱对产物进行了表征.X射线粉末衍射结果表明,产物是四方相AgCuSe;透射电镜结果表明,产物是纳米棒,其直径为5~20nm,长度为200~600nm;X射线光电子能谱结果表明,产物的纯度是很高的,没有单质Ag、Cu等杂质.应用化学热力学原理讨论了产物AgCuSe的生成机理.热力学计算表明,在这个反应体系中最终产物是纯AgCuSe.溶剂乙二胺不仅作为双齿配体与Ag+和Cu+形成稳定的配合物,而且还能溶解金属硒、增强硒的反应性,乙二胺在控制AgCuSe的成核和纳米棒的生长过程中起着重要的作用.  相似文献   
78.
A film of Ni(OH)2 deposited cathodically on a roughened nickel substrate consists of even nanoparticles, which were characterized by atomic-force microscopy (AFM). The mechanism of potential oscillations in the electrocatalytic oxidation of methanol on this film electrode in alkaline medium was studied in situ by means of Raman spectroscopy in combination with electrochemical measurements. The redox change of the nickel hydroxide film, the concentration distribution of methanol in the diffusion layer, and the oxidation products of methanol were characterized in situ by time-resolved, spatial-resolved, and potential-dependent Raman spectroscopy, respectively. Electrochemical reactions, i.e. methanol oxidation and periodic oxygen evolution, coupling with alternately predominant diffusion and convection mass transfer of methanol, account for the potential oscillations that occur during oxidation of methanol above its limiting diffusion current. This mechanism is totally different from that of methanol oxidation on platinum electrodes, for which surface steps, i.e. formation and removal of COad, are essential.This work is dedicated to Professor Gyorgy Horanyi on the occasion of his 70th birthday in recognition of his numerous contributions to field of electrochemical oscillations and electrocatalysis at Ni-hydroxide electrodes.  相似文献   
79.
原子吸收硫化锌法间接测定精氨酸络合反应的机理研究   总被引:5,自引:0,他引:5  
通过编程计算精氨酸和锌离子在不同pH条件下的各种存在形式,通过分析拟合分布图,研究了在硫化锌法原子吸收间接测定精氨酸时的pH对原子吸收响应的影响及络合反应的机理.经对不同形态的精氨酸与金属锌离子的共存区域的各种组合探讨,指出在pH 9.0左右最佳测定条件下的pH响应峰是由于精氨酸和锌离子的两种不同存在形式的变化所引起的左右峰边缘,精氨酸是以正一价荷电形态的精氨酸基Arg -与Zn(OH)2形成了可溶性络合离子[HN=CH(NH 3)-NH-(CH2)3-CH(NH 3)-COO]2Zn(OH)2.结果表明,理论分析计算的结果与实验数据得到了基本吻合,确定了硫化锌法原子吸收间接测定精氨酸时的络合物反应机理及络合物的组成结构.  相似文献   
80.
This paper shows that repetitive, infinite structures cannot be simultaneously statically, and kinematically, determinate.  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