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   1393篇
  免费   266篇
  国内免费   267篇
化学   1019篇
力学   61篇
综合类   79篇
数学   206篇
物理学   561篇
  2023年   19篇
  2022年   43篇
  2021年   68篇
  2020年   42篇
  2019年   13篇
  2018年   8篇
  2017年   7篇
  2016年   12篇
  2015年   5篇
  2014年   333篇
  2013年   298篇
  2012年   160篇
  2011年   262篇
  2010年   210篇
  2009年   214篇
  2008年   106篇
  2007年   36篇
  2006年   7篇
  2005年   10篇
  2004年   26篇
  2003年   6篇
  2002年   4篇
  2001年   2篇
  2000年   8篇
  1999年   5篇
  1998年   10篇
  1997年   2篇
  1996年   1篇
  1995年   4篇
  1993年   1篇
  1992年   2篇
  1989年   1篇
  1959年   1篇
排序方式: 共有1926条查询结果,搜索用时 15 毫秒
71.
A simple,sensitive,and reliable method for the voltammetric determination of bisphenol A(BPA) by using carboxylic group functionalized single-walled carbon nanotubes(f-SWCNT)/carboxylic-functionalized poly(3,4-ethylenedioxythiophene)(PC4) complex modified glassy carbon electrode(GCE) has been successfully developed.The electrochemical behavior of BPA at the surface of the modified electrode is investigated by electrochemical techniques.The cyclic voltammetry results show that the as-prepared electrode exhibits strong catalytic activity toward the oxidation of BPA with a well-defined anodic peak at 0.623 V in PBS(0.1 mol/L,pH 7.0).The surface morphology of the 3D network of composite film is beneficial for the adsorption of analytes.Under the optimized conditions,the oxidation peak current is proportional to BPA concentration in the range between 0.099 and 5.794 μmol/L(R~2 = 0.9989),with a limit of detection of 0.032 μmol/L(S/N = 3).The enhanced performance of the sensor can be attributed to the excellent electrocatalytic property of/-SWCNT and the extraordinary conductivity of PC4.Furthermore,the proposed modified electrode displays high stability and good reproducibility.The good result on the voltammetric determination of BPA also indicates that the asfabricated modified electrode will be a good candidate for the electrochemical determination and analysis of BPA.  相似文献   
72.
A phthalazinone monomer with an allyl group, i.e. 4-(3-allyl-4-hydroxyphenyl)phthalazin-1(2H)-one, was synthesized and then copolymerized with 4-(4-hydroxylphenyl)(2H)-phthalazin-1-one and 2,6- diflurobenzonitrile by means of aromatic nucleophilic polycondensation to provide a series of crosslinkable poly(aryl ether nitrile)s. The virgin copolymers exhibited good solubility in polar organic solvents with relative high molecular weights (Mw: 45,130-58,403, inherent viscosities: 0.58-0.75 dL/ g). After cross-linking, the thermal stability and solvent resistance of the polymer increased.  相似文献   
73.
We describe a convenient method for the synthesis of 1,2-disubstituted acetylenes via a cross-coupling reaction of (bromoethynyl)benzene with Grignard reagents. The reaction of (bromoethynyl)benzene (1 mmol) with Grignard reagent (1.3 mmol) mediated by NiCl2 (4 mol%) and (p-CH3Ph)3P (8 mol%) in THF could produce 1,2-disubstituted acetylenes in good yields at room temperature.  相似文献   
74.
In this work, MoOx promoted Ir/SiO2 catalysts were prepared and used for the selective hydrogenolysis of tetrahydrofurfuryl alcohol (THFA) to 1,5-pentanediol in a continuous flow reactor. The effects of different noble metals (Ir, Pt, Pd, Ru, Rh), supports and Ir contents were screened. Among the investigated catalysts, 4 wt%Ir-MoOx/SiO2 with a Mo/Ir atomic ratio of 0.13 exhibited the best catalytic performance. The synergy between Ix particles and the partially reduced isolated MoOx species attached on them is essential for the excellent catalytic performance of Ix-MoOx/SiO2. The catalyst exhibited a better hydrogenolysis efficiency of THFA with the selectivity of 1,5-pentanediol of 65%-74% at a conversion of THFA of 70%-75% when the initial THFA concentration is ranging from 20 wt% and 40 wt%. And higher system pressure was also in favor of the conversion of THFA. During a stability test, the conversion of THFA and 1,5-pentanediol yield over Ix-MoOz/SiO2 decreased with reaction time, which can be explained by the leaching of Mo species during the reaction.  相似文献   
75.
A series of high surface area graphitic carbon materials (HSGCs) were prepared by ball-milling method. Effect of the graphitic degree of HSGCs on the catalytic performance of Ba-Ru-K/HSGC-x (x is the ball-milling time in hour) catalysts was studied using ammonia synthesis as a probe reaction. The graphitic degree and pore structure of HSGC-x supports could be successfully tuned via the variation of ball-milling time. Ru nanoparticles of different Ba-Ru-K/HSGC-x catalysts are homogeneously distributed on the supports with the particle sizes ranging from 1.6 to 2.0 nm. The graphitic degree of the support is closely related to its facile electron transfer capability and so plays an important role in improving the intrinsic catalytic performance of Ba-Ru-K/HSGC-x catalyst.  相似文献   
76.
A new coordination compound with formula [Tb(2-TC)3(DMF)]n (1, 2-TC = 2-thio- phenecarboxylic ligand and DMF = dimethylformamide) was synthesized by solvothermal method. The structure of compound 1 was determined by single-crystal X-ray diffraction analyses, and characterized by elemental analyses, IR and powder X-ray diffraction. Structure analysis reveals compound 1, exhibiting a one-dimensional chain structure, crystallizes in triclinic space group P21/c, with a = 9.2751(19), b = 16.490(3), c = 15.865(5) A, β = 118.98(2)°, V= 2122.7(9)A3, D,. = 1.916 g/cm3, Mr= 612.45 (C18H15NO7S3Tb), F(000) = 1196,μ(MoKa) = 3.67 mm-1, Z = 4, R = 0.0616 and wR = 0.0962 for 3865 observed reflections (I 〉 2o(I)), and R = 0.1092 for all data. Meanwhile, the photoluminescent properties of compound 1 were also investigated in the solid state at room temperature.  相似文献   
77.
FarzinMarandi 《结构化学》2014,(8):1184-1190
[Pb(TPT)(μ-I)2PbI2(μ-I)2Pb(TPT)] 1(TPT is the abbreviation of 3,5,6-tris(2-pyridyl)-1,2,4-triazine ligand) has been synthesized and characterized by elemental analysis, IR, 1HNMR spectroscopy and studied by thermal and electrochemical properties as well as X-ray crystallography. The single-crystal X-ray data show two different kinds of Pb2+ ions in 1 with coordination numbers of six, Pb1 = PbI6, and five, Pb2 = PbN3I2, with holodirected and hemidirected coordination spheres, respectively. The supramolecular features in 1 are negotiated through the weak but directional Pb···I, C–H···N and C–H···I interactions and aromatic π-π stacking interactions.  相似文献   
78.
A new Cd(II) coordination polymer, namely, [Cd3(1,2,3-BTC)2(L)2]·2.25H2O (1, L = 2-(2-chloro-6-fluorophenyl)-1H-imidazo[4,5-A][1,10]phenanthroline and 1,2,3-BTC = 1,2,3-ben- zenetricarboxylate), has been synthesized under hydrothermal conditions. The compound was characterized by single-crystal X-ray diffraction. It crystallizes in triclinic, space group Pī with α = 11.650(2), b = 12.240(2), c = 19.760(4) A, α = 72.01(3), β = 77.11(3), γ = 83.48(3)°, V = 2609.4(9) A3, Z = 2, C56H31Cd3Cl2F2N8O14.25, Mr = 1489.99, Dc = 1.896 g/cm3, F(000) = 1466, μ(MoKa) = 1.401 mm^-1, R = 0.0401 and wR = 0.1104. Compound 1 shows a 1D chain structure, and the neigh- boring 1D chains of 1 are joined together by π···π interactions to result in a 2D supramolecular layer. In addition, the luminescent property of 1 has been studied in the solid state at room temperature.  相似文献   
79.
傅强 《高分子科学》2014,32(7):953-960
Poly(butylene succinate) (PBS) with different molecular weight was synthesized from 1, 4-butanediol and succinic acid by direct melt condensation. The synthesized PBS was identified by IH-NMR and FTIR spectrometry. The molecular weight was calculated from the intrinsic viscosity, and its value was between 20000 and 70000. The crystallization behavior and crystal morphology as function of molecular weight were investigated by DSC and PLM, respectively. The mechanical properties and hydrolytic degradation behaviors related with change of molecular weight were also studied in this work. The results demonstrated that the properties of PBS were determined by both molecular weight and crystallization properties (crystallinity as well as crystal morphology). Our work is important for the design and preparation of PBS with proper molecular weight for its practical application.  相似文献   
80.
程振平  朱秀林 《高分子科学》2014,32(8):1010-1018
Atom transfer radical polymerization of styrene(St) and methyl methacrylate(MMA) in bulk and in different solvents using activators generated by electron transfer(AGET ATRP) were investigated in the presence of a limited amount of air using FeCl3·6H2O as the catalyst, ascorbic acid sodium salt(AsAc-Na) as the reducing agent, and a cheap and commercially available tetrabutylammonium bromide(TBABr) as the ligand. It was found that polymerization in THF resulted in shorter induction period than that in bulk and in toluene for AGET ATRP of St, while referring to AGET ATRP of MMA, polymerization in THF showed three advantages compared with that in bulk and toluene: 1) shortening the induction period, 2) enhancing the polymerization rate and 3) having better controllability. The living features of the obtained polymers were verified by chain end analysis and chain-extension experiments.  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