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   19024篇
  免费   3598篇
  国内免费   3962篇
化学   14177篇
晶体学   310篇
力学   1129篇
综合类   330篇
数学   2624篇
物理学   8014篇
  2024年   22篇
  2023年   345篇
  2022年   533篇
  2021年   642篇
  2020年   773篇
  2019年   845篇
  2018年   663篇
  2017年   716篇
  2016年   853篇
  2015年   960篇
  2014年   1149篇
  2013年   1460篇
  2012年   1673篇
  2011年   1784篇
  2010年   1384篇
  2009年   1415篇
  2008年   1515篇
  2007年   1342篇
  2006年   1289篇
  2005年   1058篇
  2004年   847篇
  2003年   650篇
  2002年   679篇
  2001年   592篇
  2000年   525篇
  1999年   445篇
  1998年   313篇
  1997年   280篇
  1996年   246篇
  1995年   229篇
  1994年   196篇
  1993年   194篇
  1992年   149篇
  1991年   126篇
  1990年   121篇
  1989年   108篇
  1988年   92篇
  1987年   65篇
  1986年   59篇
  1985年   56篇
  1984年   45篇
  1983年   32篇
  1982年   31篇
  1981年   15篇
  1980年   8篇
  1979年   8篇
  1978年   11篇
  1977年   5篇
  1976年   5篇
  1965年   5篇
排序方式: 共有10000条查询结果,搜索用时 281 毫秒
991.
以3,5-二硝基苯甲酸(3,5-Hdnbc)和2,2′-联吡啶(2,2′-bipy)为配体,与Zn2+和Cu2+反应,得到了4个配合物[Zn(3,5-dnbc)2(2,2′-bipy)(H2O)]·(3,5-Hdnbc)(1),[Cu(3,5-dnbc)2(2,2′-bipy)(H2O)](2),[Cu(2,2′-bipy)2(3,5-dnbc)](NO3)·2(3,5-Hdnbc)(3),和[Cu(2,2′-bipy)2Cl](3,5-dnbc)·(3,5-Hdnbc)(4)。用元素分析、红外光谱对其进行了表征,并用单晶X-射线衍射测定了配合物的晶体结构;对配合物1和2进行了热重分析。4个配合物均为单核分子。配合物1中,Zn2+离子是五配位的三角双锥结构;配合物2中,Cu2+离子是五配位的变形四方锥结构;配合物3和4中,Cu2+离子均是五配位的三角双锥结构;配合物中存在氢键和π-π堆积等弱的分子间作用力。  相似文献   
992.
以3-硝基邻苯二甲酸和咪唑及2,2′-联吡啶为配体构筑了2种配合物[Zn2(npa)2(Im)4](1)和[Cd2(npa)2(2,2′-bipy)2(H2O)2]·2H2O(2)(npa2-=3-硝基邻苯二甲酸根,Im=咪唑,2,2′-bipy=2,2′-联吡啶)。用元素分析、红外光谱对其进行了表征,并用单晶X-射线衍射测定了配合物的晶体结构;测定了配合物1和2的热稳定性。2个配合物均为双核分子,具有M2C8O4十四元大环结构。配合物1的双核单元通过分子间氢键形成3D网络结构,配合物2的双核单元通过分子间氢键和π-π堆积形成2D层状结构。  相似文献   
993.
A series of novel chelating fibers containing sulfur, nitrogen, oxygen heteroatoms were prepared via the functionalization of chloromethylated polyphenylene sulfide (CMPPS). The structures, micromorpholo- gy and physicochemical properties of these fibrous adsorptive materials were characterized by FT-IR, elementary analysis, TG and SEM-EDS. The results show that chelating fibers had high functional group contents (3.94 mmol/g for thiourea, 3.85 mmol/g for mercapto, 5.00 mmol/g for methylamine and 6.07 mmol/g for ethylenediamine, respectively). Owing to the unique matrix of polyphenylene sulfide fiber, these fibrous adsorbents possess excellent thermostability. This synthetic method proved a simple and efficient way for the preparation of chelating fibers.  相似文献   
994.
Bromodimethylsulfonium bromide(BDMS) was used as an efficient brominating reagent for the synthesis of 9,10-dibromoanthracene in dichloromethane. The desired products were obtained in excellent yields.  相似文献   
995.
In recent years, there has been a pronounced interest in solid-contact ion-selective electrodes (SC-ISEs), with emphasis on the use of conducting polymers as ion-to-electron transducer. In this work, a ladder conjugated polymer, thieno[3,2-b]thiophene (LCPT), was investigated in fabricating Cu2+-selective electrodes for the first time. The resulting electrodes were characterized by electrochemical impedance spectroscopy (EIS), chronopotentiometry, and the water layer test. Results proved that the active LCPT facilitates the ion-to-electron transduction, and avoids the detrimental aqueous layer formed at the interface of SC-ISEs.  相似文献   
996.
与传统敷料相比,静电纺丝纳米抗菌敷料具有极大的比表面积和孔隙率,既有益于细胞呼吸,又可阻止细菌感染伤口,并能有效增大抗菌药物与伤口中细菌的作用面积而高效杀菌。此外,纳米敷料还能最大程度仿生细胞外基质的结构,有利于加快细胞和组织的生长,促进受损皮肤的恢复,因而非常适合用做皮肤敷料。本文对静电纺丝纳米抗菌敷料的特点,各类基体材料、抗菌药物在静纺抗菌敷料制备中的应用,以及静纺敷料的抑菌效果做了介绍,并对静电纺丝纳米抗菌敷料的应用前景做了展望。  相似文献   
997.
Sn-doped TiO_2 nanoparticles with high surface area of 125.7 m~2·g~(-1) are synthesized via a simple one-step hydrothermai method and explored as the cathode catalyst support for proton exchange membrane fuel cells.The synthesized support materials are studied by X-ray diffraction analysis,energy dispersive X-ray spectroscopy and transmission electron microscopy.It is found that the conductivity has been greatly improved by the addition of 30 mol%Sn and Pt nanoparticles are well dispersed on Ti_(0.7)Sn_(0.3)O_2 support with an average size of 2.44 run.Electrochemical studies show that the Ti_(0.7)Sn_(0.3)O_2 nanoparticles have excellent electrochemical stability under a high potential compared to Vulcan XC-72.The as-synthesized Pt/Ti_(0.7)Sn_(0.3)O_2 exhibits high and stable electrocatalytic activity for the oxygen reduction reaction.The Pt/Ti_(0.7)Sn_(0.3)O_2 catalyst reserves most of its electrochemically active surface area(ECA),and its half wave potential difference is 11 mV,which is lower than that of Pt/XC-72(36 mV) under 10 h potential hold at 1.4 V vs.NHE.In addition,the ECA degradation of Pt/Ti_(0.7)Sn_(0.3)O_2is 1.9 times lower than commercial Pt/XC-72 under 500 potential cycles between 0.6 V and 1.2 V vs.NHE.Therefore,the as synthesized Pt/Ti_(0.7)Sn_(0.3)O_2 can be considered as a promising alternative cathode,catalyst for proton exchange membrane fuel cells.  相似文献   
998.
Assisted by graphene oxide(GO),nano-sized LiMn0.6Fe0.4PO4 with excellent electrochemical performance was prepared by a facile hydrothermal method as cathode material for lithium ion battery.SEM and TEM images indicate that the particle size of LiMn0.6Fe0.4PO4(S2)was about 80 nm in diameter.The discharge capacity of LiMn0.6Fe0.4PO4 nanoparticles was 140.3 mAh-g^1 in the first cycle.It showed that graphene oxide was able to restrict the growth of LiMn0.6Fe0.4PO4 and it in situ reduction of GO could improve the electrical conductivity of LiMn0.6Fe0.4PO4 material.  相似文献   
999.
In this work, a core–shell molecularly imprinted polymer (MIP) was synthesized through sol–gel coating procedure by using silica beads, emodin, 3-aminopropyltriethoxysilane, tetraethoxysilane and tetrahydrofuran as supporting matrix, template, functional monomer, cross-linker and solvent, respectively. The selective recognition property for emodin and its analogues (physcion and aloe emodin) of the resultant MIP was evaluated in a chromatographic column for high-performance liquid chromatography (HPLC). The retention time and imprinted factor of MIP column for emodin, physcion and aloe emodin were 5.11, 0.63, 0.69 min and 4.69, 0.75, 1.38, respectively. It showed that the MIP beads had a good binding ability for emodin. Finally, one-step separation of emodin from alcohol extract of Rheum palmatum L. at semi-preparative scale was achieved and 380 mg of emodin was collected in 5 days. The product was characterized by mass spectrometry and HPLC and its purity was 95 %.  相似文献   
1000.
Eight isomorphous metal‐organic frameworks: [Ln2(TATAB)2(H2O)(DMA)6]·5H2O (Ln = Sm ( 1 ), Eu ( 2 ), Gd ( 3 ), Tb ( 4 ), Dy ( 5 ), Er ( 6 ), Tm ( 7 ), Yb ( 8 )); TATAB = 4,4′,4″‐s‐triazine‐1,3,5‐triyl‐p‐aminobenzoate, DMA = N,N‐dimethylacetamide), were synthesized by the self‐assembly of lanthanide ions, TATAB, DMA and H2O. Single‐crystal X‐ray crystallography reveals they are three dimensional frameworks with 2‐fold interpenetration. Solid‐state photoluminescence studies indicate ligand‐to‐metal energy transfer is more efficient for compounds 2 and 4 which exhibit intense characteristic lanthanide emissions at room temperature.  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