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   6805篇
  免费   602篇
  国内免费   3488篇
化学   10277篇
晶体学   43篇
力学   32篇
综合类   86篇
数学   11篇
物理学   446篇
  2024年   14篇
  2023年   125篇
  2022年   205篇
  2021年   260篇
  2020年   353篇
  2019年   384篇
  2018年   329篇
  2017年   326篇
  2016年   329篇
  2015年   318篇
  2014年   448篇
  2013年   626篇
  2012年   433篇
  2011年   524篇
  2010年   412篇
  2009年   390篇
  2008年   472篇
  2007年   469篇
  2006年   434篇
  2005年   432篇
  2004年   467篇
  2003年   397篇
  2002年   311篇
  2001年   312篇
  2000年   310篇
  1999年   247篇
  1998年   235篇
  1997年   249篇
  1996年   189篇
  1995年   191篇
  1994年   152篇
  1993年   193篇
  1992年   114篇
  1991年   62篇
  1990年   65篇
  1989年   42篇
  1988年   28篇
  1987年   16篇
  1986年   7篇
  1985年   9篇
  1984年   6篇
  1983年   5篇
  1982年   2篇
  1981年   1篇
  1979年   1篇
  1959年   1篇
排序方式: 共有10000条查询结果,搜索用时 171 毫秒
991.
The vast applications of triflic acid (TfOH) in catalysis are severely limited by its corrosive and fuming properties. Immobilization of TfOH on silica gel well solves these problems and affords efficient recovery and reusability of TfOH. Two types of supported TfOH, the prepared silica gel supported TfOH and the in situ silica gel adsorbed TfOH, both exhibit good catalytic activity and reusability in the hydroamination of alkene with sulfonamide. The in situ silica gel adsorbed catalyst has been used for 5 runs with maintained reactivities and yields, which are superior to the performance of the prepared silica gel supported TfOH. For a series of alkenes and various sulfonamides, the heterogeneous hydroamination reactions catalyzed by both types of silica gel supported TfOH to afford similar moderate to excellent yields.  相似文献   
992.
通过溶剂热法成功制备了一种基于金属有机骨架(MOF)的复合材料Cu-Cu2O/UiO-66-NH2,采用傅里叶变换红外光谱(FTIR)、X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)对材料进行全面表征。在空气作氧化剂条件下,以苯甲醇氧化为苯甲醛作为模型反应,系统地考察了溶剂、温度、催化剂各组分用量等因素对催化效果的影响。研究结果表明,该复合催化剂在醇选择性氧化反应中表现出优异的催化性能,60℃下反应5 h便可将苯甲醇定量转化为苯甲醛,并对其他苄基醇、烯丙基醇和杂芳基醇等底物也展现出良好活性。此外,循环利用3次后,该催化剂活性几乎不变,表明其具有良好的稳定性和重复使用性。  相似文献   
993.
The effect of several Lewis acids on the CBS catalyst (named after Corey, Bakshi and Shibata) was investigated in this study. While 2H NMR spectroscopic measurements served as gauge for the activation capability of the Lewis acids, in situ FT‐IR spectroscopy was employed to assess the catalytic activity of the Lewis acid oxazaborolidine complexes. A correlation was found between the Δδ(2H) values and rate constants kDA, which indicates a direct translation of Lewis acidity into reactivity of the Lewis acid–CBS complexes. Unexpectedly, a significant deviation was found for SnCl4 as Lewis acid. The SnCl4–CBS adduct was much more reactive than the Δδ(2H) values predicted and gave similar reaction rates to those observed for the prominent AlBr3–CBS adduct. To rationalize these results, quantum mechanical calculations were performed. The frontier molecular orbital approach was applied and a good correlation between the LUMO energies of the Lewis acid–CBS–naphthoquinone adducts and kDA could be found. For the SnCl4–CBS–naphthoquinone adduct an unusual distortion was observed leading to an enhanced Lewis acidity. Energy decomposition analysis with natural orbitals for chemical valence (EDA‐NOCV) calculations revealed the relevant interactions and activation mode of SnCl4 as Lewis acid in Diels–Alder reactions.  相似文献   
994.
采用TiO2上高度分散的金纳米粒子做催化剂,从脂肪族硝基化合物、醛和氢气可高选择性合成硝酮。与碳负载Pt催化剂相比,该催化体系上硝酮的选择性从50%增加到90%。其催化性能可有活性位结构、载体特性和反应条件精确调节。  相似文献   
995.
The activity of [Pd(C6H4CH2 NH2‐κ2‐C‐N)PPh3MOBPPY]OTf complex, A (MOBPPY = 4‐methoxybenzoylmethylenetriphenyl‐ phosphoraneylide), was investigated in the Heck–Mizoroki C? C cross‐coupling reaction under conventional heating and microwave irradiation conditions. The complex is an active and efficient catalyst for the Heck reaction of aryl halides. The yields were excellent using a catalytic amount of [Pd(C6H4CH2 NH2‐κ2‐C‐N)PPh3MOBPPY]OTf complex in N‐methyl‐2‐pyrrolidinone (NMP) at 130 °C and 600 W. In comparison to conventional heating conditions, the reactions under microwave irradiation gave higher yields in shorter reaction times. Copyright © 2010 European Peptide Society and John Wiley & Sons, Ltd.  相似文献   
996.
Chiral Jacobsen's catalysts grafted onto alkoxyl‐modified ZPS‐PVPA exhibit excellent activities (conv%, up to 96; sele%, up to 96; ee%, up to >99) in the asymmetric epoxidations of unfunctionalized olefins. The superior stabilities and the comfortable dispositions in large‐scale reactions contribute to the potential applications in industry.  相似文献   
997.
Bis(indolyl)alkanes have been synthesised in excellent yields in the presence of catalytic amount of silica-supported Preyssler nano particles as green, reusable and efficient catalyst under ultra sonic irradiation.  相似文献   
998.
《中国化学会会志》2017,64(8):896-917
β‐Cyclodextrin (β‐CD ), a naturally occurring supramolecular structure, is an effective catalyst for the synthesis of heterocyclic compounds. Its ubiquity, high performance, nontoxicity, ease of separation, and reusability have drawn the attention of green chemists. Here we present the synthetic procedures of heterocyclic compounds catalyzed by β‐CD in water and compare them with those using organic solvents. In many cases, using water as the solvent shows better efficiency than conventional organic solvents with regard to catalytic activity and simplicity of recycling procedures. This review highlights the applications of β‐CD in catalysis covering the years 2004–2016.  相似文献   
999.
A soluble,poly(ethylene glycol)-supported piperazine catalyst was prepared.This soluble catalyst efficiently catalyzes the Knoevenagel condensation of various aromatic aldehydes with diethyl malonate or ethyl acetoacetate in a homogeneous phase to afford the desired alkenes in good purity and yield with a facile work-up process.It was found that the polymer reagent could be repeatedly used at least four times without the too much loss of activity.The catalyst has shown a good activity,stability,and recyclin...  相似文献   
1000.
Ag3PW12O40 and Ag4SiW12O40 showed high activity and stability in the synthesis of diethylene glycol ethyl ether with diethylene glycol and ethanol, on which the conversion is 80.2% and 78.4%, respectively, and the selectivity of diethylene glycol ether is 75.4% and 80.6%, respectively. After the third reaction cycle, Ag3PW12O40 and Ag4SiW12O40) still showed higher activity and selectivity, on which the conversion is 72. 6% and 77.5% respectively. But the activity of Ag3PMo12O40 is lower, the conversion is only 21.0%. IR, XRD, TG and n‐butylamine titrimetry showed that the catalysis may be connected with two kinds of acidic centers owned by heteropoly acidic salt.  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