首页 | 官方网站   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   3893篇
  免费   811篇
  国内免费   761篇
数理化   5465篇
  2024年   24篇
  2023年   102篇
  2022年   163篇
  2021年   261篇
  2020年   371篇
  2019年   228篇
  2018年   198篇
  2017年   154篇
  2016年   224篇
  2015年   225篇
  2014年   242篇
  2013年   389篇
  2012年   247篇
  2011年   257篇
  2010年   171篇
  2009年   202篇
  2008年   220篇
  2007年   241篇
  2006年   211篇
  2005年   175篇
  2004年   142篇
  2003年   152篇
  2002年   99篇
  2001年   78篇
  2000年   95篇
  1999年   61篇
  1998年   69篇
  1997年   62篇
  1996年   57篇
  1995年   66篇
  1994年   50篇
  1993年   40篇
  1992年   52篇
  1991年   30篇
  1990年   28篇
  1989年   19篇
  1988年   16篇
  1987年   6篇
  1986年   12篇
  1985年   4篇
  1984年   5篇
  1983年   6篇
  1982年   2篇
  1981年   4篇
  1980年   1篇
  1977年   1篇
  1976年   1篇
  1975年   1篇
  1973年   1篇
排序方式: 共有5465条查询结果,搜索用时 203 毫秒
71.
It was shown that metallcontaining peroxides such as XOOOBu-t [X = (t-BuO)2Al, (t-BuO)3Ti] generate molecular oxygen in the electron-excited singlet state (1O2). These ozonides and η2-peroxocomplex Ph3Bi(η2O2) demonstrate high oxidative activity towards some classes of organic substances under mild conditions (20 °C).  相似文献   
72.
The reaction of C2H6with lattice oxygen, O2- (in the absence of gaseous oxygen), or “adsorbedℍ oxygen (in the presence of gaseous oxygen) over NiMoO4 catalysts has been performed and compared to C3H8 activation. The results obtained indicate that adsorbed oxygen exhibits a higher reactivity to C2H6, while lattice oxygen is more reactive relative to C3H8. Kinetic studies of these two reactions in presence of molecular oxygen have indeed shown that the ethane oxidative dehydrogenation (ODH) is dependent on the oxygen partial pressure, whilst on the contrary propane ODH is not. In order to confirm the presence of “adsorbed” oxygen for ethane activation, ODH tests have been performed with N2O. On increasing temperature, the O- adsorbed species enhances the mild oxidation of ethane. The activation energy of ethane consumption EC2H6, relative to propane (EC3H8 = 133 kJ/mol) is 145 kJ/mol. A possible mechanism is proposed for the oxidative dehydrogenation of ethane. This revised version was published online in August 2006 with corrections to the Cover Date.  相似文献   
73.
在甲烷氧化偶联(OCM)反应条件下,用原位红外光谱研究SrO-La2O3/CaO催化剂,结果表明,晶格氧使甲深度氧化,La2O3和CaO具有活泼的晶格氧,SrO的晶格氧比较稳定,气相氧通过催化剂表面消耗掉的晶格氧,加速甲烷了深度氧化,另一方面,催化剂表面的碳酸根物种在氧气氛下分解,在La2O3和LC催化剂中,催化剂表面La2O2(CO3)的分解形成配位不饱和的晶格氧O^2-,并为气相氧吸附提供氧空  相似文献   
74.
IntroductionInthcsclcctivcoxidationofalkanes.suchas'theoxidativccouplingofmcthanc(0CM)andthcoxidativcdch}'drogenationofcthanc(0DE)t0prcparccth}'lene.bothoxidcionsofthelatticeandtheox}'genspeciesovercataIystsuffocepla}'animportantrole.Althoughcxtcnsivcinvcstigationshavcbeengivcntothecharactcrizationofox}'gcnspccicsandthcreactionofox}'gcnspecicsx`ithalkanes,itisstilldifficulttosayt`hichoncsofox}'gcnspcciesarcthcactivcspecicsinthcactivation0falkancs.bccauscthenaturcofcatal}'stsandthecxperimcntc…  相似文献   
75.
Recent work has indicated that Ormosil films, fabricated from organically modified precursors, produce better sensor performance for some specific applications, compared to films fabricated from conventional sol-gel precursors such as TEOS or TMOS. This paper aims to compare film properties and sensor behavior for films fabricated from tetraethoxysilane (TEOS) and tetramethoxysilane (TMOS) silica precursors and both methyltrimethoxysilane (MTMS) and methyltriethoxysilane (MTES) organically modified precursors. Microstructural differences, for example, porosity changes due to the different precursor backbone structures, are interrogated by monitoring oxygen gas and aqueous-phase sensor response. Oxygen sensing using these films is enabled by incorporating in the films an oxygen-sensitive ruthenium dye whose fluorescence is quenched in the presence of oxygen. Film properties such as thickness, thickness stabilization time, as well as sensor response, are discussed in terms of relative hydrolysis and condensation behavior for the different precursors. Film hydrophobicity, an issue which has been identified as being of crucial importance for optimum dissolved oxygen sensor response, is discussed and contact angle measurements are used to investigate the degree of hydrophobicity for different film types. The main motivation for this work is film optimization for optical gas-phase and dissolved oxygen sensors.  相似文献   
76.
环境水中化学需氧量的FI分光光度法自动在线检测   总被引:10,自引:0,他引:10  
本文将流动注射分光光度法用于环境废水中化学需氧量(COD)的自动在线检测,方法线性范围在0-100mg/L之间,相对标准偏差<2%以葡萄糖和苯二甲酸氢钾混合液制备标准溶液,对标准参考水样COD含量(Cr值)的测定结果表明两者有良好的相关性(R=0.9880)对环境水样中COD含量的动态变化连续10h模拟试验,自制的在线过滤装置稳定,未发生堵塞现象;该系统可以较好地跟踪水样中COD浓度的实际变化  相似文献   
77.
为了改善镍电极的高温充电效率,采用机械混合的方式将球形Ni(OH)2与不同比例的Lu2O3混合后制成粘结式镍正极。充放电测试、循环伏安和XRD等实验结果表明,掺杂Lu2O3后镍电极的析氧过电位明显提高,高温充电效率得到了很大改善,在充电后的电极中β-NiOOH生成;而且Lu2O3的掺杂比例对镍电极的高温性能在不同的充放电倍率下有不同程度的影响,3.5%是最好的掺杂比例,掺杂对高温小电流充电效率的改善作用要大于高温大电流充电。  相似文献   
78.
The oxidative polycondensation of 4-[(pyridin-3-ylimino)methyl]phenol (4-PIMP) with O2, H2O2, and NaOCl was studied in an aqueous alkaline medium between 50°C and 90°C. Oligo-4-[(pyridin-3-ylimino)methyl]phenol (O-4-PIMP) prepared was characterized by 1H-NMR, 13C-NMR, FT-IR, UV-VIS, size-exclusion chromatography, and elemental and thermal analyses techniques. At the optimum reaction conditions, the yield of O-4-PIMP was 18.9%, 39.4%, and 46.8% using H2O2, O2, and NaOCl oxidant, respectively. According to the TG analysis, the initial degradation temperature of O-4-PIMP was 218°C, which was by 50°C higher than that of 4-PIMP. Thermal analyses of 4-PIMP and O-4-PIMP were carried out in N2 atmosphere at 15–1000°C. The highest occupied molecular orbital, the lowest unoccupied molecular orbital, and electrochemical energy gaps of 4-PIMP and O-4-PIMP were determined from the onset potentials for n-doping and p-doping, respectively. Also, optical band gaps of 4-PIMP and O-4-PIMP were determined according to UV-VIS measurements.  相似文献   
79.
用TPD-MS、TPSR-MS及CO氧化活性测定等方法研究了Pt/Al2O3和掺杂超细ZrO2的样品的表面氧脱出-恢复性能、CO表面氧化性能及催化氧化性能.结果表明,在Pt/Al2O3中掺杂ZrO2后,样品表面上的氧物种脱出和氧化恢复性能明显提高,脱氧量也明显增大;并发现在CO-TPSR过程中程脱物CO2的脱附量大小及峰顶温度次序与对CO的催化氧化活性也有一致的关系  相似文献   
80.
低分子量溴代聚苯乙烯的制备及应用   总被引:5,自引:0,他引:5  
用溶液法合成了一系列低分子量的聚苯乙烯,其溴化产物(Br-PS)的溴含量和热稳定性与美国同类产品Pyro-Chek LM相当,分别用作聚苯乙烯树脂的阻燃剂,极限氧指数测定结果表明,其阻燃性也达到了Pyro-Chek LM的水平。  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-23

京公网安备 11010802026262号