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   5333篇
  免费   739篇
  国内免费   1433篇
化学   6316篇
晶体学   49篇
力学   100篇
综合类   34篇
数学   15篇
物理学   991篇
  2024年   10篇
  2023年   68篇
  2022年   146篇
  2021年   174篇
  2020年   259篇
  2019年   184篇
  2018年   180篇
  2017年   188篇
  2016年   293篇
  2015年   279篇
  2014年   310篇
  2013年   540篇
  2012年   400篇
  2011年   381篇
  2010年   346篇
  2009年   350篇
  2008年   342篇
  2007年   379篇
  2006年   352篇
  2005年   313篇
  2004年   340篇
  2003年   283篇
  2002年   211篇
  2001年   183篇
  2000年   155篇
  1999年   116篇
  1998年   132篇
  1997年   113篇
  1996年   91篇
  1995年   93篇
  1994年   68篇
  1993年   52篇
  1992年   30篇
  1991年   28篇
  1990年   16篇
  1989年   21篇
  1988年   24篇
  1987年   13篇
  1986年   5篇
  1985年   15篇
  1984年   7篇
  1983年   3篇
  1982年   4篇
  1981年   3篇
  1980年   2篇
  1979年   1篇
  1972年   1篇
  1967年   1篇
排序方式: 共有7505条查询结果,搜索用时 234 毫秒
101.
高温下硅酸锂吸收CO2的研究   总被引:3,自引:0,他引:3       下载免费PDF全文
以SiO2和Li2CO3为反应原料,采用高温固相法于不同温度下合成了一系列可在高温500~750 ℃之间直接吸收CO2的硅酸锂(Li4SiO4)材料。采用扫描电子显微镜(SEM)、X射线粉末衍射仪(XRD)分别观察和评价了合成材料的表面形貌与结构特征,用热重分析仪(TG)研究了硅酸锂材料吸收CO2的性能。实验结果表明,在750 ℃下煅烧6 h即可合成出吸收CO2性能良好的硅酸锂材料,在CO2气氛下,于700 ℃保持约15 min即可达到吸收平衡,其吸收量约达43%(wt)左右。与文献报道相比,材料的合成条件有所改善,材料吸收CO2的容量也有较大提高。  相似文献   
102.
CO2氧化丙烷脱氢MoO3-V2O5/SiO2催化剂研究   总被引:4,自引:0,他引:4  
采用表面改性和等体积浸渍法制备了MoO3-V2O5/SiO2复合氧化物,采用TPR、IR、TPD和微反技术表征了催化剂对CO2和C3H8的吸附性能和CO2部分氧化丙烷脱氢的反应性能.结果表明:随MoO3加入量的增加,V=O还原温度降低,晶格氧更易活化.CO2和丙烷的活化温度降低,丙烷转化率增高,丙烯选择性下降.V=O中晶格氧的活化是CO2氧化丙烷制丙烯反应的关键.  相似文献   
103.
Metal foams, now one of research foci, are a newclass of materials with low densities and novel physi-cal, mechanical, thermal, electrical and acoustic prop-erties[1—8]. Demands from high-tech make Al alloyfoam, which has much higher specific strength than ofpure Al foam, the new development focus[9—11]. Melt foaming process is one of the approaches tofabricate Al foam and Al alloy foam and their porestructure (pore diameter and porosity) has close rela-tionship with the thermal decompo…  相似文献   
104.
Chaozhang Huang 《Talanta》2007,73(2):274-281
Mesoporous titanium dioxide as a novel solid-phase extraction material for flow injection micro-column preconcentration on-line coupled with ICP-OES determination of trace metals (Co, Cd, Cr, Cu, Mn, Ni, V, Ce, Dy, Eu, La and Yb) in environmental samples was described. Possessing a high adsorption capacity towards the metal ions, mesoporous titanium dioxide has found to be of great potential as an adsorbent for the preconcentration of trace metal ions in samples with complicated matrix. The experimental parameters including pH, sample flow rate, volume, elution and interfering ions on the recovery of the target analytes were investigated, and the optimal experimental conditions were established. Under the optimized operating conditions, a preconcentration time of 90 s and elution time of 18 s with enrichment factor of 10 and sampling frequency of 20 h−1 were obtained. The detection limits of this method for the target elements were between 0.03 and 0.36 μg L−1, and the relative standard deviations (R.S.D.s) were found to be less than 6.0% (n =7, c =5 ng mL−1). The proposed method was validated using a certified reference material, and has been successfully applied for the determination of the afore mentioned trace metals in natural water samples and coal fly ash with satisfactory results.  相似文献   
105.
Mansonone compounds represent a series of naturally occurring o-quinones mainly isolated from the heartwood of Mansonia Altissima1 and Ulmus Glabra2. Mansonone F contained oxaphenalene skeleton which was a relatively novel structure and rarely existed in …  相似文献   
106.
Silica-polyimide microcomposite membranes were prepared on γ-alumina-coated α-alumina support tubes, and their gas permeation properties were evaluated with He, N2 and CO2. Smoothing of the substrate surface and hybridization of silica and polyamic acid were both effective to form defect-free thin composite membranes. The CO2 permeance of a membrane with a silica content of 68 wt% was one order of magnitude higher than that of a polyimide membrane having the same thickness. The permselectivity of CO2 to N2 was 30 at 30°C and 13 at 100°C. Contributions of the silica and polyimide phases to permeance of the composite membrane were analyzed with a two-phase permeation model. The effective thickness of the rate-controlling polyimide phase was less than one-tenth of the total thickness of the silica-polyimide membrane.  相似文献   
107.
A new hydroformylation of alkenes using carbon dioxide as a reactant is shown to take place in the presence of ruthenium cluster complexes and halide salts. Similar or even better yields of alcohols were formed as compared to the conventional hydroformylation with CO under the same reaction conditions. The reaction proceeded in three steps: CO2 is first converted to CO; then it is used as a reagent for hydroformylation to give aldehyde; subsequently, it is hydrogenated to alcohol. ESI-mass spectrometric analyses of the reaction solutions indicated formation of four kinds of ruthenium anionic complexes including tetra-, tri-, and mononuclear species. On the basis of experimental findings, possible roles of these complexes are discussed.  相似文献   
108.
甲烷二氧化碳介质阻挡放电转化产物分布研究   总被引:7,自引:0,他引:7  
针对介质阻挡放电甲烷二氧化碳转化实验,分析了反应的产物分布,探讨了进料组成和反应器结构对反应的影响.反应产物包括:高H2/CO摩尔比的合成气、气态烃、高辛烷值的汽油组分、醇和酸等含氧有机物.对所述电极结构,产物的选择性随碳数增加而降低;高的甲烷进料浓度有利于烃的生成,对醇和酸的最佳甲烷进料体积分数范围在67.4%~75.1%;放电间隙越小,原料转化率和烃、酸的选择性越大,大的放电间隙对醇的生成有利.  相似文献   
109.
IntroductionIthasbccndcmonstratcdthatmcthancrcformingt"ithcarbondioxidcpr0ducessynthcsisgasrichincarbonmonoxidc-x"hichisuscfulforthcs}nthcsisofaccticacid'dimcthylcthcrando.o-alcoholsll'2].Carbondioxidcref0rmingismorccndothcrmicthanstcamrcformingfCH4 CO2,'2CO 2H2Ai/'2,,=2473kJ..ol-1(l)Accordingl\"thisrcact1onnccdshighcrtcmpcraturcandlimitsspaccvclocityoffccdgas,Wehavcprct'ious1\studicdmcthancrcformingt"lthC02inthcmonotubcproccssl3J.Inordertoconvcrtmcthancinfccdgascomplctcl}',thcspaccvcloci…  相似文献   
110.
The relation of thermodynamic stability and kinetic lability of σ-organometallic compounds of transition metals, together with an improved understanding of the subtle interactions between central metal, ligands, and substrates, has increased the chemist's ability to plan organometallic syntheses. This article presents new results on intermediary and isolable synthetic building blocks incorporating metal–ligand multiple bonds of electron-deficient transition metals; the main emphasis will be placed on compounds with titanium–carbon double bonds. This particular class of compounds is mainly generated by H-transfer reactions starting from readily accessible alkyl and alkenyl derivatives. The preparative use of [L2Ti(CHR2)R′] derivatives as sources for [L2Ti?CR2] intermediates will be discussed, as well as the nature of these intermediates. Application of the same approach to vinyltitanium compounds [L2Ti(CH?CH2)R] opens up an access to a short-lived metallaallene derivative [L2Ti?C?CH2] of an electron-deficient transition metal. The reactivity of these synthetic building blocks is mainly characterized by the nucleophilic properties of the α-C atoms as well as by the spatial orientation of the π-bonding planes. Numerous cycloaddition products with unsaturated substrates could be isolated and characterized for the first time by using [L2Ti?C?CH2] intermediates. Hence it is possible to compare the properties of a multitude of metallacyclic ring systems with those obtained from “Tebbe–Grubbs chemistry”, and in this context, the dependence of the properties of metallacyclic four-membered rings on the substitution pattern is discussed. This class of compounds includes the metallaoxetanes, which have been obtained for the first time by the cycloaddition of the [CpTi?C?CH2] intermediate with cumulenes and metal carbonyls. The differing cycloreversion behavior of these metallaoxetanes enables the differentiation of species exhibiting classical and nonclassical reactivity. The number and position of the exocyclic double bonds are the determining factors of the reactivity of the formed metallacycles. The discussion of the products obtained from titanium methylene and vinylidene building blocks is an up-to-date report on the formation and applications of carbene complexes and carbene intermediates of group 4 metals.  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