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   7385篇
  免费   627篇
  国内免费   2350篇
化学   6362篇
晶体学   45篇
力学   1054篇
综合类   126篇
数学   1580篇
物理学   1195篇
  2024年   24篇
  2023年   84篇
  2022年   139篇
  2021年   222篇
  2020年   303篇
  2019年   278篇
  2018年   239篇
  2017年   274篇
  2016年   371篇
  2015年   281篇
  2014年   360篇
  2013年   674篇
  2012年   471篇
  2011年   465篇
  2010年   409篇
  2009年   442篇
  2008年   430篇
  2007年   527篇
  2006年   463篇
  2005年   506篇
  2004年   531篇
  2003年   428篇
  2002年   381篇
  2001年   321篇
  2000年   285篇
  1999年   239篇
  1998年   192篇
  1997年   150篇
  1996年   146篇
  1995年   144篇
  1994年   125篇
  1993年   99篇
  1992年   74篇
  1991年   53篇
  1990年   47篇
  1989年   31篇
  1988年   25篇
  1987年   27篇
  1986年   12篇
  1985年   16篇
  1984年   16篇
  1983年   6篇
  1982年   10篇
  1981年   6篇
  1980年   6篇
  1979年   9篇
  1978年   6篇
  1977年   4篇
  1976年   4篇
  1973年   4篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
91.
Sm修饰的Ni-MgO催化剂制备碳纳米管的研究   总被引:2,自引:0,他引:2  
李克  吕功煊  刘建福 《无机化学学报》2005,21(10):1571-1575
Carbon nanotubes (CNTs) have been synthesized over Ni-MgO and Ni-Sm-MgO catalysts by decomposition of CH4 at 650 ℃. The addition of Sm into Ni-MgO catalyst not only promotes the catalytic activity and lifetime of the catalyst, but also improves the graphitization and heat stability of carbon nanotubes. The yield of CNTs obtained over the Ni-10Sm-MgO catalyst reaches 33 g C·(g Ni)-1, being more than 5 times higher than that of the Ni-MgO catalyst. XRD and TPR results of the catalysts indicate that there is a remarkable interaction of Ni with Sm species, which facilitates the reduction of nickel and restrains the Ni particles from agglomerating.  相似文献   
92.
甲烷磺酸盐的合成、表征及其催化酯化反应的性能   总被引:15,自引:0,他引:15  
Methane-sulfonate of copper, cobalt, zinc, lanthanide, praseodymium and neodymium are synthesized and characterized by FTIR and TGA. Methane-sulfonates are used as the catalysts in the esterification of chloroacetic acid with isopropanol. Catalytic activity of methane-sulfonates is studied and compared with other Lewis acids. Under the condition of 1.2/1 molar ratio of isopropanol to chloroacetic acid, 1% catalyst (molar percent of chloroacetic acid), 2.5h reaction time, 80~85℃ temperature and benzene as water-carrying agent. The experi-mental results showed that catalytic activity of Lanthanide methane-sulfonate was the best, the yield of isopropyl chloroacetate reaches 88.7%. Copper methane-sulfonate can be reused for three times without distinct loss of catalytic activity.  相似文献   
93.
Fe-Ni-B-O纳米合金的合成及其催化制氢性能的研究   总被引:2,自引:0,他引:2  
Preparation and catalytic performance of Fe-Ni-B-O nano-alloy having crystal-palpus structure has been studied. Black powder was synthesized by reducing mixture solution of Fe2+, Ni2+ with KBH4 as reducing agent and polyethylene glycol as dispersant. Fe-Ni-B-O nano-alloy of crystal-palpus structure was obtained after hydrogen reduction of black powder. TEM shows that crystal-palpus length is 200~400 nm, diameter is 2~4 nm. The analytic results indicate that the total content of Fe and Ni is 86.6%, B is 5.08%. The alloy exhibits excellent catalytic performance. Hydrogen generation rate can approach 100% especially when pH is 8.  相似文献   
94.
任飞  李秋小 《催化学报》2007,28(9):829-834
以水合肼和硼氢化钾为共还原剂制备了四元合金催化剂Ni-Cu-Co-La,并将其应用于乙腈催化加氢反应.采用X射线衍射、X射线光电子能谱、透射电镜和H2程序升温脱附对催化剂进行了表征,考察了催化剂组分对乙腈选择性加氢制乙胺催化性能的影响.结果表明,Cu,Co和La的加入均不同程度地提高了催化剂的活性和选择性,在反应压力1.8 MPa,反应温度120℃,反应时间1 h的条件下,乙腈转化率和乙胺选择性分别为100%和98.24%,优于使用Raney Ni、非晶态Ni-B和Co-B合金催化剂时的结果.  相似文献   
95.
The phase diagram of the ternary system Cr-Mo-O in air was established from the results of thermal analysis of mixtures with different initial CrO3 to MoO3 ratios. It was found that MoO3 did not take any chromium oxide into solid solution. The presence of Cr2O3 destabilized MoO3 causing it to decompose to MoO2 in the temperature range 723-958 K depending on the initial Cr/Mo ratio. The decomposition of pure MoO3 MoO2 did not occur in air at any temperature. However, this decomposition took place through the formation of the compound Cr2O3·3MoO3(ss) and its decomposition to Cr2O3·3MoO2(ss). The latter compound has never been reported before and the X-ray data for this compound are given. The previously reported catalytic activity of Cr2O3·3MoO3(ss), at high temperatures, is presumably due to its reduction to Cr2O3·3MoO2(ss). This revised version was published online in July 2006 with corrections to the Cover Date.  相似文献   
96.
在滴汞电极上研究了硝基苯、对硝基甲苯、间二硝基苯及2,4-二硝基氯苯的电化学行为,并用量子理论对四种硝基苯化合物的反应活性进行了预测,理论与试验结果基本一致,据此提出了预测分子的电化学活性的方法。  相似文献   
97.
李辉  马春景  李和兴 《中国化学》2006,24(5):613-619
采用KBH4化学还原法制备了超细Ru-B非晶态合金催化剂。Ru-B催化剂在肉桂醇液相常压加氢中显示出较高的肉桂醇选择性。在加氢过程中使用超声辐射能大大提高反应速率而肉桂醇的选择性几乎保持不变。加氢速率随着超声频率或超声时间的增加而增加。通过XRD、XPS、TEM、BET和ICP等各种表征手段,简要研究了超声辐射对Ru-B催化剂结构和电子特征的影响。同时,还讨论了超声对肉桂醛选择性加氢制肉桂醇催化性能的促进作用。  相似文献   
98.
催化裂化USY/ZnO/Al2O3脱硫添加剂的高温水热失活   总被引:3,自引:0,他引:3  
 对USY/ZnO/Al2O3汽油催化裂化脱硫添加剂经高温水热老化处理前后的脱硫性能进行了考察,发现老化后添加剂的脱硫性能大幅度下降.采用XRD和IR等技术对USY/ZnO/Al2O3添加剂在高温和高温水热条件下失活的原因进行了研究.结果表明,在高温下,ZnO可与USY沸石中的铝发生固相反应生成ZnAl2O4尖晶石,从而造成USY晶体结构崩塌,转变成无定形状态.在ZnO含量较高的条件下,ZnO可继续与USY晶体结构崩塌后生成的无定形的硅和铝的氧化物反应,生成Zn2SiO4硅锌矿和ZnAl2O4尖晶石结构.这一方面使添加剂失去了可形成硫化物吸附中心的ZnO,另一方面破坏了硫化物的裂化活性组分USY,从而造成添加剂脱硫性能下降甚至失去脱硫活性.ZnO对USY的破坏作用主要与温度有关.在USY/ZnO/Al2O3体系中,ZnO被ZnO与Al2O3之间形成的锌铝尖晶石膜固定并与USY隔离,单纯的高温条件对添加剂的破坏不显著,而水蒸气可以促进ZnO的移动,有利于ZnO与USY的接触,因此在高温和有水蒸气存 在的条件下添加剂的结构易遭到破坏.  相似文献   
99.
The thermal behavior of synthetic schoenite (K2SO4·MgSO4·6H2)) during heating has been studied by thermal methods. The temperatures of dehydration and decomposition of schoenite have also been determined by DTA, TG and DSC. The thermal reaction equations and the X-ray power diffraction results of the products have been given and the corresponding kinetic parameters have also been obtained.  相似文献   
100.
In this paper, the spectral behavior of protein and Poniacyl Carmine 2B (PC 2B) has been studied by spectrophotometric method. The conditional constants, apparent combination constant K and maximum binding number n, were used to express the combination ability of the reactions between PC 2B and protein under a set of given conditions. The Sandell index s was used to express the sensitivity of the determination of protein. The factors, acidity, PC 2B concentration and the ionic strength, were discussed by the change of apparent combination constant and maximum binding number. It was found that acidity of the solution, PC 2B concentration and ionic strength had a significant effect on the sensitivity of the assay of protein. Under the optimal conditions, the apparent combination constant K and the maximum binding number n were 2.36 × 106 L mol?1 and 95, respectively. With further investigation, it was found that the Scatchard model was suitable in treating the data obtained in the experiments. In the buffer medium of HCl‐KCl at 1.87, the addition of protein made the maximum absorption of the system move from 527 nm to 513 nm. Its apparent molar absorptivity is 4.46 × 105 Lmol?1 cm?1 at 513 nm. Beer's law is obeyed in the range of 0 ? 55 μg mL?1. The system developed in this paper has been used for the determination of protein in milk powder successfully.  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