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   1511篇
  免费   124篇
  国内免费   313篇
化学   1355篇
晶体学   50篇
力学   39篇
综合类   2篇
数学   29篇
物理学   473篇
  2024年   1篇
  2023年   51篇
  2022年   57篇
  2021年   50篇
  2020年   37篇
  2019年   53篇
  2018年   35篇
  2017年   75篇
  2016年   50篇
  2015年   68篇
  2014年   72篇
  2013年   122篇
  2012年   112篇
  2011年   113篇
  2010年   95篇
  2009年   159篇
  2008年   109篇
  2007年   119篇
  2006年   95篇
  2005年   62篇
  2004年   71篇
  2003年   45篇
  2002年   51篇
  2001年   42篇
  2000年   45篇
  1999年   23篇
  1998年   25篇
  1997年   29篇
  1996年   13篇
  1995年   7篇
  1994年   16篇
  1993年   10篇
  1992年   13篇
  1990年   3篇
  1989年   6篇
  1988年   3篇
  1987年   2篇
  1985年   2篇
  1982年   2篇
  1980年   1篇
  1979年   3篇
  1976年   1篇
排序方式: 共有1948条查询结果,搜索用时 15 毫秒
71.
72.
采用程序升温反应法制备了钝化态、还原钝化态和新鲜态Mo2C/γ-Al2O3催化剂,结合原位红外光谱表征技术和反应性能评价,考察、比较了三种催化剂苯加氢反应活性.原位红外光谱结果表明,新鲜态Mo2C/γ-Al2O3催化剂在室温就显示了较好的苯加氢反应活性,表现了类贵金属的催化活性.CO吸附在反应前后新鲜态Mo2C/γ-Al2O3催化剂上的对比结果表明,低价态的Mo位(Moδ+(0δ2))是苯加氢反应活性中心.三种催化剂的反应活性结果表明,新鲜态Mo2C/γ-Al2O3催化剂反应活性最好,催化剂寿命最长,失活之后在500°C下H2处理即可恢复原有活性.  相似文献   
73.
采用自组装生长聚苯乙烯胶体模板和溶胶-凝胶法,制备出三维(3D)有序结构In掺杂TiO2(IO-TiO2-In)薄膜可见光催化剂.光催化实验证明,IO-TiO2-In薄膜降解甲醛的可见光活性是TiO2和三维有序结构TiO2(IOTiO2)薄膜的5倍.利用X射线电子衍射(XRD)谱、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)和紫外-可见(UV-Vis)漫反射吸收光谱确定了催化剂的晶相结构、表面微结构和能带结构.结果表明,IO-TiO2-In薄膜具有锐钛矿型三维有序结构,与TiO2相比,增加了比表面积,提高光的利用率;掺入的In离子在薄膜表面形成In2O3和O-In-Clx(x=1,2)物种,既增强可见光的吸收,又有效地促进了光生载流子的分离,提高了光生载流子在固/气界面参加光催化反应的利用率,使催化剂的可见光催化活性显著提高.  相似文献   
74.
沈帅  王秀丽  丁倩  金少青  冯兆池  李灿 《催化学报》2014,(11):1900-1906
采用CO作为探针分子,将原位透射红外光谱应用于研究助催化剂Pt在Pt/TiO2光催化体系中的作用.实验发现,光照条件下,CO的覆盖度及样品温度没有明显变化,CO在Pt/TiO2上的吸附峰红移11 cm–1,在Pt/Al2O3上的吸附峰没有位移,表明CO在Pt/TiO2上的红移来源于TiO2上的光生电子转移到Pt上,这解释了为什么加入Pt助催化剂可提高光催化产氢活性.  相似文献   
75.
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   
76.
陈婷  管斌  林赫  朱霖 《催化学报》2014,35(3):294-301
采用自蔓延燃烧法制备了Ti0.9Mn0.05Fe0.05O2-δ催化剂,运用原位漫反射傅里叶变换红外光谱对该催化剂的NO和NH3稳态吸附以及NO和NH3瞬态反应进行了详细地分析与讨论. 结果表明,相比于Lewis酸性位,150℃时Brönsted酸性位吸附的NH3更具有SCR活性;与双齿硝酸盐和桥式硝酸盐相比,NO吸附产生的单齿硝酸盐是主要的中间物种;该SCR反应遵循Eley-Rideal和Langmuir-Hinshelwood机理,但以后者为主. 另外,O2的存在有利于NO的氧化和配位态NH3的活化.  相似文献   
77.
Cu(In,Ga)Se2 absorbers were immerged in deionized water for different times, and specific chemical evolutions were monitored thanks to X-ray photoemission spectroscopy. Cu(In,Ga)Se2 related dissolution products were studied in water through induced coupled plasma optical emission spectroscopy. From those analyses, specific surface network disorganization was observed, with Cu migration towards the surface, leading to different kinetics of oxidation and dissolution for each element that could be quantified.  相似文献   
78.
A series of silver-doped cerium zirconium oxide(Ag-CexZr) samples was synthesized successfully for selective catalytic reduction of nitric oxide(NO) with hydrogen and propene(H2/C3H6-SCR) under excess oxygen condition. The catalytic activity test proved that Ag-Ce0.4Zr exhibited the best C3H6-SCR activity. Hydrogen(H2) significantly enhanced NO conversion and widened the temperature window. Multi-technology characterizations were conducted to ascertain the properties of fabricated catalysts including X-ray diffraction(XRD), Fourier transform infrared spectrometry(FTIR), scanning electron microscopy(SEM) and H2 temperature programmed reduction (H2-TPR). In situ FTIR results demonstrated that various types of nitrates and chelating nitrite were generated on Ag-CexZr after introduction of NO. Besides, adding H2 could increase the concentration of bidentate nitrate and chelated bidentate nitrate dramatically, especially for Ag-Ce0.4Zr catalyst. Transient reaction between pre-adsorbing NO and C3H6/C3H6+H2 illuminated that the most active intermediate was chelating nitrite,which was promoted significantly by H2 participation. Furthermore, adding H2 improved the formation of organo-nitro(R-NO2), which was the key intermediate in C3H6-SCR. The reaction mechanism over Ag-CexZr catalysts was proposed at 200℃ as follows:nitric oxide(NO)+propene(C3H6)+hydrogen(H2)+oxygen(O2)→chelating nitrite(NO2-)+acrylate-type species(CxHyOz)→organo-nitro(R-NO2)→isocyanate(-NCO)+cyanide(-CN)→nitrogen(N2).  相似文献   
79.
Developing new types of rechargeable batteries with high energy densities and low cost have received increasing attentions, aiming to reduce the dependence on high-priced lithium. Beyond Li-ion batteries, the potential alternatives including Na-ion batteries, Li-S batteries and Li-air batteries have been investigated recently, which are required to be viable for commercial applications. From this point of view, to understand the electrochemical reaction mechanisms and kinetics of these batteries has become the key challenge to make breakthroughs in the field of new energy storage. In this review, we present a critical overview of the two dimensional nanomaterials-based batteries (except Li-ion-based batteries) that could meet such demonds. To develop new energy storage devices with more promising performances, the microstructure evolution and atomic scale storage mechanism of these batteries are comprehensively summarized. In addition, the major challenges and opportunities of advanced characterization techniques are finally discussed. We do hope that this review will give the readers a clear and profound understanding of the electrochemical reaction mechanisms and kinetics of the as-discussed batteries, thus effectively contributing to the smart design of future-generation energy storage devices.  相似文献   
80.
BackgroundOncogenic human papilloma viruses (HPV) are the cause of various types of cancer, specifically cervical cancer. L1 protein is the main protein of HPV capsid which targeted in many vaccine-producing attempts. However, they have not enough coverage on the various high risk HPV types. Therefore, having a low cost potent HPV vaccine to protect against all members of the α-papillomaviridea family will be promising. In this study, L1 protein-based peptide vaccine was designed using immunoinformatics methods which provides physicochemical properties such as stability in room temperature, potential of antigenicity, non-allergic properties and no requirement with eukaryotic host system.ResultsThe designed vaccine has two HPV conserved epitopes with lengths 18 and 27 amino acids in all members of α-papillomaviridea. These peptides promote humoral and cellular immunity and INF-γ responses. In order to ensure strong induction of immune responses, Flagellin, a Toll like receptor 5(TLR-5) agonist, and a short synthetic toll like receptor 4 (TLR-4) agonist were also joined to the epitopes. Structure of the designed- vaccine was validated using Rampage and ERRAT and a high quality 3D structure of the vaccine protein was provided. Docking studies demonstrated an appropriate and stable interaction between the vaccine and TLR-5.ConclusionsThe vaccine is expected to have a high quality structure and suitable properties including high stability, solubility and a high potential to be expressed in E.coli. High potentiality of the vaccine in inducing humoral and cellular immune responses, may be considered as an anti-tumor vaccine.  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