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   1862篇
  免费   205篇
  国内免费   40篇
电工技术   12篇
综合类   37篇
化学工业   1246篇
金属工艺   187篇
机械仪表   17篇
建筑科学   4篇
矿业工程   18篇
能源动力   33篇
轻工业   12篇
水利工程   1篇
石油天然气   119篇
武器工业   1篇
无线电   52篇
一般工业技术   163篇
冶金工业   154篇
原子能技术   41篇
自动化技术   10篇
  2024年   8篇
  2023年   16篇
  2022年   26篇
  2021年   35篇
  2020年   35篇
  2019年   34篇
  2018年   38篇
  2017年   68篇
  2016年   119篇
  2015年   65篇
  2014年   114篇
  2013年   164篇
  2012年   141篇
  2011年   121篇
  2010年   87篇
  2009年   85篇
  2008年   96篇
  2007年   118篇
  2006年   91篇
  2005年   91篇
  2004年   82篇
  2003年   62篇
  2002年   72篇
  2001年   66篇
  2000年   50篇
  1999年   49篇
  1998年   33篇
  1997年   21篇
  1996年   26篇
  1995年   12篇
  1994年   21篇
  1993年   9篇
  1992年   13篇
  1991年   5篇
  1990年   20篇
  1989年   1篇
  1988年   3篇
  1987年   2篇
  1986年   1篇
  1985年   1篇
  1984年   2篇
  1983年   1篇
  1982年   1篇
  1981年   2篇
排序方式: 共有2107条查询结果,搜索用时 15 毫秒
41.
A series of new ion exchange resins was synthesized in a microwave radiation field by modification of chloromethylated styrene/divinylbenzene (S/DVB) and vinylbenzylchloride/divinylbenzene (VBC/DVB) copolymers using amines. The modification processes have been executed simultaneously using the microwave-assisted method and the most efficient, conventional one. The greatest total sorption capacities for noble metals were achieved for two resins conventionally modified using ETDA ion exchange resins based on S/DVB matrices. The microwave-modified resins reveal only slightly lower and in some circumstances even better sorption capacity for noble metals than their conventionally-modified equivalents. The differences are discussed by effect of the synthesis method as evaluated using FTIR spectrophotometry.  相似文献   
42.
An efficient palladium‐catalyzed decarboxylative ortho‐acylation of 2‐aryloxypyridines with α‐oxocarboxylic acids is described. In this new transformation, the aromatic C(sp2) H bond was successfully acylated to give diverse aromatic ketones regioselectively in moderate to good yields. The pyridine group can be removed easily after the acylation to give the corresponding 2‐hydroxy aromatic ketones.  相似文献   
43.
The PdCl(C3H5)(dppb)/KOAc system was found to be effective for the direct regioselective C‐5 arylation of 3‐acetylpyrroles with ortho‐substituted aryl bromides. This procedure has been found to be tolerant to a variety of functional groups at C‐2 of the aryl bromide such as methyl, formyl, nitrile, nitro, hydroxymethyl, chloro, fluoro or trifluoromethyl. The sequential direct C‐5 arylation followed by C‐2 arylation of such 3‐substituted pyrroles allows the synthesis of 2,5‐diaryl‐3‐acetylpyrroles in high yields.  相似文献   
44.
Tetra(arylalkynyl)pyridines and tetra(arylalkenyl)pyridines and their benzene analogues were prepared by palladium‐catalyzed cross‐coupling reactions from the commercially available chlorinated substrates in good to excellent yields. The photophysical properties of selected compounds were investigated and compared to each other. Very good fluorescence quantum yields were observed, especially for the pyridine derivatives.  相似文献   
45.
A series of novel 2-aryl1-4-bromothiophenes (2a–f), biarylthiophenes with non-identical aryl groups (3a–e) and biarylthiophenes with identical aryl groups (4a–f) were synthesized in moderate to excellent yields by using different arylboronic acids in a Suzuki–Miyaura cross-coupling reaction. The experimental results showed that the use of K2CO3 as base resulted in moderate yields compared with that of good yields obtained upon using K3PO4. The highest yield obtained using K3PO4 was 82% for 2, 4-bis (4-chlorophenyl) thiophene (4d). The synthesized compounds in the present study were examined for their biofilm inhibition and hemolysis assay. Among all compounds 2, 4-bis (4-methoxyphenyl) thiophene (4b) was found to strongly inhibit the formation of bacterial biofilm against E. coli. The compound 4b exhibited higher inhibition (80.92%) compared with the standard Rifampicin with 97.43% inhibition. The compound 2, 4-bis (4-chlorophenyl) thiophene (4d) displayed strong anti-biofilm activity with its ability to prevent the formation of Pasteurell amultocida biofilm at the percent inhibition of 74.53%. In addition, 2f showed the highest percentage hemolysis 16.0% compared with that of the standard Triton-X-100. 3  相似文献   
46.
《Catalysis Reviews》2013,55(4):593-649
Palladium-based catalysts are widely applied in exhaust catalytic converter and catalytic combustion systems. The mechanism for methane oxidation on a Pd-based catalyst is complex. Catalyst activity is influenced by variations in the process pressure and temperature, by the gas mixture composition, by the type of support and various additives, and by pretreatment under reducing or oxidizing atmospheres. In this paper, we review the literature on supported Pd catalysts for combustion of methane. The mechanisms involved are discussed taking into consideration the oxidation/reduction mechanisms for supported palladium, poisoning, restructuring, the form of oxygen on the surface, methane activation over Pd and PdO phases, and transient behavior. Our review helps explain the array of experimental results reported in the literature.  相似文献   
47.
3,5-二羟基苯甲酸转移加氢动力学   总被引:3,自引:0,他引:3  
研究了3,5-二羟基苯甲酸(DHB)为原料采用催化转移加氢法合成3,5-二氧代环己烷羧酸(DOC)的过程,得到了以5%Pd/C为催化剂、甲酸钠为氢供体的3,5-二羟基苯甲酸转移加氢宏观反应动力学。研究发现,在实验条件下原料3,5-二羟基苯甲酸的反应级数为0,供体甲酸钠和催化剂分别为一级;当氢供体大量过量时,3,5-二羟基苯甲酸的吸附速率是反应的控速步骤,初步探讨了反应过程的机理。  相似文献   
48.
采用以过渡金属Pd(Ⅱ)为活性中心的催化体系,催化一氧化碳(CO)与苯乙烯(St) 、对乙基苯乙烯(ESt)的间歇共聚合反应,得到具有规整结构的交替共聚产物STCO 和ESTCO.动力学研究表明, ESt比St具有更高的共聚合反应活性,但在间歇聚合条件下失活较早,表现为ESt需要较高的CO压力与之相匹配,说明烯烃的活性越高,所需的CO压力区间也越高.由于在苯环上引入对乙基基团,ESTCO与STCO相比,熔点和结晶度略有下降,但在有机溶剂中的溶解性增强.  相似文献   
49.
江峰  余卫国 《浙江化工》2005,36(5):26-28
采用绿色合成法,在水相条件下,在Pd/C催化剂的作用下用苯甲酸催化氢化合成环己基甲酸.通过一系列的实验,得到了较好的合成环己基甲酸的工艺条件,在该条件下,能够得到比较纯的产物和较好的产物收率.  相似文献   
50.
p-Methylphenylalkylsulfide of various alkyl chain length as extractant were synthesized and the extraction of palladium was examined in terms of equilibrium and kinetics. Distribution ratio of Pd was independent of alkyl chain length. For aqueous chloride media, there was a significant difference in distribution ratios for the solution of NaC1 and HC1. The results of loading test and the slope analysis suggest that the extractant and Pd (Ⅱ) form 2:1 complex. Furthermore, the extraction rate based on the volume of aqueous phase was obtained in a stirred vessel, and the rate equation was presented. Unfortunately, it was difficult to construct surfactant liquid membrane system by use of the present extractant.  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