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   2639篇
  免费   354篇
  国内免费   2066篇
化学   3699篇
晶体学   92篇
力学   51篇
综合类   79篇
数学   172篇
物理学   966篇
  2024年   46篇
  2023年   166篇
  2022年   162篇
  2021年   160篇
  2020年   124篇
  2019年   133篇
  2018年   111篇
  2017年   107篇
  2016年   111篇
  2015年   90篇
  2014年   224篇
  2013年   173篇
  2012年   200篇
  2011年   192篇
  2010年   162篇
  2009年   189篇
  2008年   217篇
  2007年   225篇
  2006年   219篇
  2005年   185篇
  2004年   200篇
  2003年   153篇
  2002年   142篇
  2001年   169篇
  2000年   115篇
  1999年   144篇
  1998年   132篇
  1997年   120篇
  1996年   100篇
  1995年   87篇
  1994年   92篇
  1993年   80篇
  1992年   85篇
  1991年   63篇
  1990年   54篇
  1989年   64篇
  1988年   18篇
  1987年   13篇
  1986年   9篇
  1985年   15篇
  1984年   5篇
  1983年   2篇
  1981年   1篇
排序方式: 共有5059条查询结果,搜索用时 31 毫秒
131.
制备了负载铬酸氢根的季铵树脂,研究了以该树脂为氧化剂将糠醇氧化为糠醛的反应,考察了温度,时间、溶剂,树脂与醇的摩尔比对该氧化反应的影响。在优化反应条件下,即以苯为溶剂,n(树脂):n(醇)=3.5:1,反应回流10h,糠醛产率达75%,实验中铬酸氢根季铵树脂选择性地将糠醇氧化为糠醛,表明它是一种有效的、可套用的氧化剂。  相似文献   
132.
常贯儒  周立新陈动 《中国化学》2006,24(11):1514-1522
A systematic quantum chemical characterization of intrinsic structure, energies and spectral properties of all the studied cross-link adducts formed by the novel trans platinum with thiazole ligand has been carried out at B3LYP/6-31G^* level of theory with the Lanl2dz pseudo potential basis set for the Pt atom. Special attention has been paid to the relative stability of these complexes and the factors that probably alter the order of the relative stability. The important influence of hydrogen bond on the structures, the energies and the spectral property was revealed. Other factors that contribute to relative stability including solvation effect, entropy and electronic delocalization energy were taken into account. The stability energy of the whole complex, and the interaction energy between two purine bases and the [Pt-(NH3)thiazole]^2+ group were adopted to study the interplay among subsystems and their contribution to relative stability of all the studied cross-link model. Finally, basic spectral properties of these complexes including H(8) chemical shifts of all the studied complexes and the VCD (vibrational circular dichroism) spectra of two pairs of GG chelate enantiomers, were provided in order to define the structure of the most possible duplex bearing novel trans platinum drug lesions.  相似文献   
133.
连芬燕  王瑞虎  韩磊  洪茂椿 《结构化学》2005,24(9):1039-1042
1 INTRODUCTION The rational design and synthesis of new metal- organic coordination polymers have generated con- siderable interest in supramolecular chemistry and material science owing to their intriguing structural diversities and potential applications as functional materials[1~3]. Molecular self-assembly has been pro- ved to be an efficient way to construct various inte- resting coordination polymers[4~6]. The coordina- tion covalent bond, hydrogen bond or other mole- cular interact…  相似文献   
134.
In the 21st century, hydrogen energy is a novel energy source. Its use is expected to mitigate the problems of environmental pollution and global warming caused by the excessive use of conventional fossil fuels. The hydrogen evolution reaction (HER) for water splitting has attracted considerable attention because of its environmental friendliness. To improve electrocatalyst performance and reduce operation cost, carbon-based metal hybrid materials exhibiting high efficiency and catalytic activity have been developed. Among them, carbon dots (CDs) have garnered significant research attention and have been widely applied in biosensing, bioimaging, and energy conversion/storage because of their facile synthesis, biocompatibility, tunable photoluminescence, excellent stability, and good electronic properties. CDs are widely used as carriers in the construction of electrocatalysts prepared from carbon-based metal hybrid materials. At present, it is believed that CDs exhibit excellent confinement effects, which can effectively inhibit the growth and agglomeration of metal nanoparticles, thereby preparing well-distributed carbon-based metal hybrid materials with a uniform and controllable size. However, the formation process of the small-molecule raw materials of CDs has not been elucidated. In this study, CDs and small-molecule raw materials from synthetic CDs were used as precursors to prepare nitrogen-doped CD-supported ruthenium nanoparticle (Ru@CDs) and small-molecule-supported ruthenium nanoparticle (Ru@Molecule) hybrid materials, respectively. The interaction between the small molecules and Ru in the process of CD formation and the effect on HER performance were explored. Moreover, we prepared different carriers such as metal organic frameworks(MOF), carbon nanotubes (CNTs), and graphene (GO)-supported ruthenium nanoparticle hybrid materials. Among them, Ru@CDs exhibited controllable size and excellent dispersibility and exhibited outstanding HER activity and good stability. Ru@CDs were found to require a low overpotential of 22 mV to reach a current density of 10 mA·cm−2. Moreover, we observed the presence of an intermediate state between the molecules and CDs and demonstrated that the intermediate state exhibits no confinement effect. Furthermore, we found that with increasing calcination temperature, the intermediate state gradually changes to CDs. The unique spatial confinement between CDs and metal ions is key to the formation of monodisperse Ru nanoparticles. Our results confirmed that Ru@CDs serve as excellent HER catalyst supports. This work not only reveals the effect of the unique spatial confinement of CDs on the supported metals and their promoting effect on electrocatalytic activity but also provides guides the future development of CD-based metal hybrid electrocatalysts.  相似文献   
135.
曾锋  崔昆燕 《分析化学》1995,23(11):1323-1325
本研究了铀-2-(3,5-二溴-2-吡啶偶氮)-5-二乙氨基苯酚(3,5-diBr-PADAP)-Tri-ton-X-100析相光度体系,建立了矿石中微量铀的测定方法。在PH7.5三乙醇胺-盐酸介质中,将胶束溶液在95±1℃。络合物即被Triton-X-100相完全富集。  相似文献   
136.
若干3d过渡金属的硫代脯氨酸配合物   总被引:4,自引:0,他引:4  
合成了七个新的过渡金属的硫代脯氨酸(tcH)配合物,它们分别是:[M(tc)_2](M=Mn(Ⅱ),Co((Ⅱ))和Ni(Ⅱ)),[Ni(tc)(Ac)(H_2O)],[Ni(tc)(tcH)(H_2O)]NO_3·H_2O,[Ni(tc)(Py)_2(H_2O)NO_3和[Fe(tc)_2(Cl)(H_2O)]。上述配合物的磁化率,摩尔电导,热量分析,红外及电子光谱数据表明,它们都具有八面体构型,tcH主要通过亚氨氮和羧基氧原子与金属键合。文章对这些配合物的可能结构作了初步的讨论。  相似文献   
137.
本文以烯烃、芳烃、多核芳烃、烯烃-烷烃混合物、烯烃-多核芳烃混合物、氯代烃和溴代烃等类型的化合物为代表, 考察了化合物结构对气相色谱-微波等离子体发射光谱联用测定化合物经验式结果的影响。对属于同系物的烃类选其中任一种为参比物, 测定准确度不受化合物结构的影响; 对含有非同系物的混合物, 如烯烃-多核芳烃, 参比物和被测物的结构对测定结果准确度有一定的影响, 选择其中的非同系物作参比物时, 所测得的经验式准确度相对较差; 含卤素原子的化合物结构对经验式测定影响较大, 必须选择结构相近(碳架结构和卤素原子数相近)的化合物作为经验式测定的参比物。  相似文献   
138.
研究了用B掺杂替代Al对AB5型稀土贮氢合金相结构和电化学性能的影响。对M1Ni3.55Co0.75Mn0.4Al0.3-xBx(x=0,0.1,0.2,0.3)合金的研究结果表明:掺B后贮氢合金出现了CeCo4B第二相,导致贮氢合金的电化学容量下降;随B含量的增加和Al含量的减少,氢的扩散系数明显上升,合金的极化电阻减小,合金的高倍率放电性能和低温性能得到明显改善。  相似文献   
139.
Pt3Co核-Pt壳型纳米粒子的制备及磁性   总被引:1,自引:1,他引:1  
Pt3Co alloy nanoparticles were prepared by the reduction of H2PtCl6 and Co(OOCCH3)2 using NaBH4 as a reducing agent. The Pt3Co core-Pt shell nanoparticles (Pt3Co@Pt) were synthesized using hydrogen absorption reduction and characterized by plasma-atomic emission spectrometry (ICP), transmission electron microscopy (TEM), X-ray diffraction (XRD) and SQUID magnetometer. The results show that average size of Pt3Co@Pt nanoparticles is 3.6 nm with a standard deviation of 0.9 nm. Heating Pt3Co nanoparticles in air at 700 ℃ for 1 h, Co in Pt3Co nanoparticles was oxidized to Co3O4 and CoO; while no oxidation tendency was detected for Pt3Co@Pt nanoparticles. The crystallize structure of Pt3Co@Pt changed from the face centered cube (fcc) to the face centered tetragonal (fct) after the heating treatment. The coercivity of the heated Pt3Co@Pt reached to 276 Oe at room temperature.  相似文献   
140.
以KF-蒙脱土为催化剂, 取代肉桂腈与5,5-二甲基-1,3-环己二酮在95%乙醇中回流反应得2-氨基-3-氰基-4-芳基-7,7-二甲基-5-氧代-4H-5,6,7,8-四氢苯并[b]吡喃, 此方法快速、方便、高效, 同时考察了溶剂、催化剂对反应的影响.  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