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   269篇
  免费   15篇
  国内免费   3篇
化学   224篇
晶体学   5篇
力学   2篇
数学   17篇
物理学   39篇
  2023年   10篇
  2022年   9篇
  2021年   10篇
  2020年   10篇
  2019年   13篇
  2018年   11篇
  2017年   8篇
  2016年   16篇
  2015年   10篇
  2014年   6篇
  2013年   24篇
  2012年   26篇
  2011年   22篇
  2010年   16篇
  2009年   18篇
  2008年   11篇
  2007年   10篇
  2006年   6篇
  2005年   15篇
  2004年   1篇
  2003年   5篇
  2002年   1篇
  2001年   4篇
  2000年   1篇
  1999年   3篇
  1998年   5篇
  1996年   1篇
  1994年   2篇
  1993年   1篇
  1991年   1篇
  1986年   1篇
  1984年   5篇
  1982年   3篇
  1981年   1篇
  1980年   1篇
排序方式: 共有287条查询结果,搜索用时 31 毫秒
31.
Novel covalently crosslinked membranes based on sulfonated poly(ether ether ketone) and carboxylated polysulfone exhibit much lower methanol crossover and better performance in direct methanol fuel cells at 65 °C in 1 and 2 M methanol solutions compared to Nafion 115 membranes.  相似文献   
32.
The substitution of a small amount of Ga in the high-voltage spinel cathode LiMn1.5Ni0.42Ga0.08O4 leads to superior cyclability at room temperature and 55 °C along with higher rate capability with conventional electrolytes compared to that found with the LiMn1.5Ni0.5O4 cathode. The superior performance is attributed to the segregation of the inert Ga3+ ions to the surface during the synthesis process, providing a robust, more stable interface with the electrolyte at the high operating voltage (~ 4.7 V), along with the stabilization of the spinel structure with a disordering of the cations in the octahedral sites.  相似文献   
33.
In this study, the antimicrobial effect and DNA gyrase inhibitor potential of vanillin-based pyridyl–substituted fluoro-indolines were evaluated. These compounds are synthesized and established through green-chemistry approaches. The inhibition effect on both DNA gyrase A and B was evaluated in silico and in vitro. Agar well diffusion method–based antimicrobial activity against Gram-ve Pseudomonas aeruginosa (MTCC 424) and Escherichia coli (MTCC 443), Gram+ve Streptococcus pyogenes (MTCC 442) and Staphylococcus aureus (MTCC 96), and a clinical isolate of Candida albicans (Fungi) was evaluated. The cytotoxicity of the compounds was assessed over macrophages using the MTT assay. In the results, the target compounds exhibited a broad-spectrum antimicrobial activity against both bacterial types and fungal.  相似文献   
34.
The catalytic activity of carbon supported Pd-Co-Mo for the oxygen reduction reaction (ORR) in a single cell proton exchange membrane fuel cell (PEMFC) has been investigated at 60 degrees C and compared with data from commercial Pt catalyst and our previously reported Pd-Co-Au and Pd-Ti catalysts. The Pd-Co-Mo catalyst with a Pd:Co:Mo atomic ratio of 70:20:10 exhibits slightly higher catalytic activity like the Pd-Co-Au catalyst than the commercial Pt catalyst, but with excellent chemical stability unlike the Pd-Co-Au catalyst. The Pd-Co-Mo catalyst also exhibits better tolerance to methanol poisoning than Pt. Investigation of the catalytic activity of the Pd-Co-Mo system with varying composition and heat treatment temperature reveals that a Pd:Co:Mo atomic ratio of 70:20:10 with a heat treatment temperature of 500 degrees C exhibits the highest catalytic activity. Although the degree of alloying increases with increasing temperature from 500 to 900 degrees C as indicated by the X-ray diffraction data, the catalytic activity decreases due to an increase in particle size and a decrease in surface area.  相似文献   
35.
High yielding syntheses of 1‐(ferrocenylmethyl)‐3‐mesitylimidazolium iodide ( 1 ) and 1‐(ferrocenylmethyl)‐3‐mesitylimidazol‐2‐ylidene ( 2 ) were developed. Complexation of 2 to [{Ir(cod)Cl}2] (cod=cis,cis‐1,5‐cyclooctadiene) or [Ru(PCy3)Cl2(?CH‐o‐O‐iPrC6H4)] (Cy=cyclohexyl) afforded 3 ([Ir( 2 )(cod)Cl]) and 5 ([Ru( 2 )Cl2(?CH‐o‐O‐iPrC6H4)]), respectively. Complex 4 ([Ir( 2 )(CO)2Cl]) was obtained by bubbling carbon monoxide through a solution of 3 in CH2Cl2. Spectroelectrochemical IR analysis of 4 revealed that the oxidation of the ferrocene moiety in 2 significantly reduced the electron‐donating ability of the N‐heterocyclic carbene ligand (ΔTEP=9 cm?1; TEP=Tolman electronic parameter). The oxidation of 5 with [Fe(η5‐C5H4COMe)Cp][BF4] as well as the subsequent reduction of the corresponding product [ 5 ][BF4] with decamethylferrocene (Fc*) each proceeded in greater than 95 % yield. Mössbauer, UV/Vis and EPR spectroscopy analysis confirmed that [ 5 ][BF4] contained a ferrocenium species, indicating that the iron center was selectively oxidized over the ruthenium center. Complexes 5 and [ 5 ][BF4] were found to catalyze the ring‐closing metathesis (RCM) of diethyl diallylmalonate with observed pseudo‐first‐order rate constants (kobs) of 3.1×10?4 and 1.2×10?5 s?1, respectively. By adding suitable oxidants or reductants over the course of a RCM reaction, complex 5 was switched between different states of catalytic activity. A second‐generation N‐heterocyclic carbene that featured a 1′,2′,3′,4′,5′‐ pentamethylferrocenyl moiety ( 10 ) was also prepared and metal complexes containing this ligand were found to undergo iron‐centered oxidations at lower potentials than analogous complexes supported by 2 (0.30–0.36 V vs. 0.56–0.62 V, respectively). Redox switching experiments using [Ru( 10 )Cl2(?CH‐o‐O‐iPrC6H4)] revealed that greater than 94 % of the initial catalytic activity was restored after an oxidation–reduction cycle.  相似文献   
36.
Fuel cells are appealing for a variety of energy needs, but the high materials and manufacturing costs have hampered their commercialization. The limited availability and the high cost of the currently used platinum catalysts, for example, pose a serious problem in their practical application. We report here non-platinum electrocatalyst systems, such as Pd-Co-Au and Pd-Ti, that are proposed from simple thermodynamic guidelines and selected by a rapid screening technique, which show electrochemical performance in proton exchange membrane fuel cells (PEMFC) similar to that found with commercial platinum catalysts. This finding opens up a new avenue to develop potentially less expensive electrocatalysts.  相似文献   
37.
The proton NMR spectrum of benzo[b]furan has been investigated in the nematic phase of a liquid crystal. Dipolar couplings obtained from the spectral analysis have been used to derive the interproton distance ratios. The phenyl ring geometry differs from that in benzo[b]thiophene. The deviations have been explained in terms of bond polarization effects.  相似文献   
38.
39.
JPC – Journal of Planar Chromatography – Modern TLC - Arnebia nobilis has gained an increasing popularity for the recently recognized various pharmacological activities. The root part...  相似文献   
40.
A unique sodium sulfide (Na2S) cathode is developed, which will allow the use of sodium‐free anodes for room‐temperature sodium–sulfur (Na–S) batteries. To overcome the “inert” nature of the Na2S, a special cathode structure is developed by spreading the multi‐walled carbon nanotube (MWCNT)‐wrapped Na2S particles onto MWCNT fabrics. Spectroscopic and electrochemical analyses reveal a series of polysulfide intermediates involved in the charge/discharge of the cell. The Na–S battery prepared in full discharge state with the Na2S/MWCNT cathode provides a remarkable capacity of 500 A h kg?1 (based on sulfur mass) after 50 cycles.  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