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   1568篇
  免费   80篇
  国内免费   68篇
电工技术   16篇
综合类   51篇
化学工业   770篇
金属工艺   158篇
机械仪表   6篇
建筑科学   6篇
矿业工程   12篇
能源动力   278篇
轻工业   21篇
石油天然气   94篇
武器工业   2篇
无线电   63篇
一般工业技术   137篇
冶金工业   38篇
原子能技术   40篇
自动化技术   24篇
  2024年   4篇
  2023年   37篇
  2022年   43篇
  2021年   35篇
  2020年   55篇
  2019年   59篇
  2018年   40篇
  2017年   61篇
  2016年   37篇
  2015年   38篇
  2014年   74篇
  2013年   81篇
  2012年   88篇
  2011年   110篇
  2010年   77篇
  2009年   93篇
  2008年   97篇
  2007年   103篇
  2006年   88篇
  2005年   68篇
  2004年   47篇
  2003年   50篇
  2002年   46篇
  2001年   61篇
  2000年   55篇
  1999年   35篇
  1998年   29篇
  1997年   14篇
  1996年   25篇
  1995年   13篇
  1994年   14篇
  1993年   12篇
  1992年   9篇
  1991年   1篇
  1990年   9篇
  1989年   4篇
  1986年   1篇
  1980年   3篇
排序方式: 共有1716条查询结果,搜索用时 31 毫秒
161.
Pb-free solderable surface finishing is essential to implement Pb-free solder assembly in order to meet with the growing demand of environmental consciousness to eliminate Pb from electronic products. Two types of widely applicable Pb-free surface finishing technologies are developed. One is the multilayer-system including Pd with Ni undercoat. Heat-resistance of Pd enables whole-surface-plating on to leadframe before IC-assembling process. The other is the double-layer-system with low-melting-point-materials, for example, thicker Sn underlayer and thinner Sn-Bi alloy overlayer, dilutes Sn-Bi alloy’s defects of harmful reactivity along with substrate metal and mechanical brittleness with keeping its advantages of solder-wettability and no whisker.  相似文献   
162.
Herein, well-dispersed Palladium (Pd) nanoparticles (NPs) with good catalytic activities were prepared using a wood nanomaterial (WNM) as a reductant and a supporting agent. Various factors that influenced the NP morphologies, including reaction time, temperature, and precursor concentration were studied. The as-prepared Pd NPs/WNM showed good catalytic performance for Suzuki coupling reactions.  相似文献   
163.
Makoto Misono   《Catalysis Today》2009,144(3-4):285
Recent progresses in practical applications of (i) supported heteropolyacid and (ii) Pd/perovskite catalysts are described. (i) Two industrial catalytic processes, ethyl acetate and acetic acid syntheses both from ethylene, utilize silicotungstic acid, alone and together with Pd, respectively, carefully supported on silica, and exhibit high performance from green chemical and economical viewpoints. The layer structure of heteropolyacid on silica and physical properties of silica are among the key factors of the high performance. (ii) Pd/perovskite catalyst is applied for the treatment of automotive emission, where the catalyst life is very much elongated by embedding Pd into the perovskite lattice and hence resulted in much reduced usage of Pd. These are good examples of green catalytic technology that will contribute to the sustainable society.  相似文献   
164.
The catalytic activity of [PdCl2(NH2(CH2)12CH3)2] (named [Pd(TDA)]) and [RhCl(NH2(CH2)12CH3)3] (named [Rh(TDA)]) complexes for the hydrogenation of cyclohexene has been analysed both in homogeneous phase and heterogenised on activated carbon. The [Rh(TDA)] complex has been found to be more active than the [Pd(TDA)], both homogeneous and heterogenised. Experimental and modelled results indicate that these complexes follow a similar reaction mechanism, but with different rates. A clear positive effect of the carbon support has been found in the case of the complex [Rh(TDA)], which has been related to the anchorage of the aliphatic chains of the amine ligands on the activated carbon pores. Experiments in consecutive catalytic runs show that the heterogenised complexes can be used several times giving an acceptable conversion level.  相似文献   
165.
Theoretical studies of CO hydrogenation to methanol over Cu, Pd, and Pt metals have been carried out using a quasi‐relativistic density‐functional method. The metal surface is simulated by a M10 cluster model. Reaction energies for the elementary steps involved are determined. The activation energies are estimated by the analytic BOC‐MP formula. The results support that these metals are active in CO hydrogenation to methanol. The rate‐determining steps are shown to be different for the metals. The highest activation energies of reaction on the metals fall in the order Cu < Pd < Pt, which corresponds to the order of the catalytic activities of the metals in CO hydrogenation. This revised version was published online in July 2006 with corrections to the Cover Date.  相似文献   
166.
Supported Pd or Rh catalysts were prepared by the solid-phase crystallization method starting from hydrotalcite anionic clay minerals based on [Mg6Al2(OH)16CO 2 2− ]·4H2O as the precursors. The precursors were prepared by a coprecipitation method from the raw materials containing Pd2+ and various trivalent metal ions which can replace each site of Mg2+ and Al3+ in the hydrotalcite. Rh3+ was also used for preparing the catalyst as comparison. The precursors were then thermally decomposed and reduced to form supported Pd or Rh catalysts and used for the methanol decomposition to synthesis gas. Among the precursors tested, use of Mg–Cr hydrotalcite containing Pd2+ resulted in the formation of efficient Pd supported catalysts for the production of synthesis gas by selective decomposition of methanol at low temperature. Although Pd2+ cannot well replace the Mg2+ site in the hydrotalcite, the Pd supported catalyst (Pd/Mg–Cr) prepared by the solid-phase crystallization method formed highly dispersed Pd metal particles and showed much higher activity than that prepared by the conventional impregnation method. When the precursor was prepared under mild conditions, more fine particles of Pd metal were formed over the catalyst, resulting in high activity. It is likely that the high activity may be due to the highly dispersed and stable Pd metal particles assisted by the role of Cr as the co-catalyst. This revised version was published online in November 2006 with corrections to the Cover Date.  相似文献   
167.
Molecular dynamics simulations have been performed to investigate the thermal expansivity of MgO at high temperature using the very similar Lewis-Catlow and Stoneham-Sangster shell model potentials. In order to take account of non-central forces in crystals, the breathing shell model is also introduced in simulation. The volume thermal-expansion coefficient αP of MgO dependence of the temperature T at 0 and 135 GPa have been obtained and compared with the available experimental and theoretical results. Compared with shell model potentials, the molecular dynamics results obtained using breathing shell model potentials are more compressible. At an extended pressure and temperature ranges, αP has also been predicted.  相似文献   
168.
以Pd/C为催化剂直接催化氢化2-氨基-4,6-二羟基-5-亚硝基嘧啶削备2,5-二氨基-4,6-羟基嘧啶,采用正交设计方法考察了碱的浓度、溶剂、催化剂用量、温度、反应时间等对反应的影响,收率在86%以上。  相似文献   
169.
引 言催化反应在化学合成中占有极为重要的地位 [1] .最近 ,等离子体技术在催化剂制备领域的应用在发达国家受到广泛重视 [2~ 4 ] .利用等离子体技术制备的催化剂具有很多优点 ,例如大的比表面积、高分散性、晶格缺陷、活性组分单一等特性 .等离子体技术对催化剂表面改性可以  相似文献   
170.
The enantioselective hydrogenation of N-acetyl dehydrophenylalanine methyl ester (NADPME) to N-acetyl phenylalanine methyl ester is investigated using cinchonine-modified Pd/TiO2 catalysts. The catalysts were prepared using deposition–reduction and wet impregnation methods and were evaluated for reaction using methanol as solvent with various cinchonine/NADPME molar ratios. Enantioselectivity was sensitive to this ratio and comparison with Pd/γ-Al2O3 showed that the Pd/TiO2 gave marginally higher enantioselectivity when tested under comparable conditions. The effect of Pd loading and dispersion was investigated and the maximum enantiomeric excess observed was dependent on the dispersion; the role of the Pd particle size is discussed in the context of cinchonine adsorption. The reactions were carried out in solvents (methanol and dimethyl formamide) and mixed solvents (methanol–water and dimethyl formamide–water); the enantiomeric excess was significantly enhanced using dimethyl formamide. The addition of water does not have a significant effect for the Pd/TiO2 catalysts. In this paper we report the highest enantiomeric excess for the hydrogenation of a prochiral ester using an immobilised catalyst.  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