首页 | 官方网站   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   44641篇
  免费   445篇
  国内免费   809篇
工业技术   45895篇
  2015年   184篇
  2014年   339篇
  2013年   290篇
  2012年   3986篇
  2011年   4866篇
  2010年   1060篇
  2009年   730篇
  2008年   3666篇
  2007年   3415篇
  2006年   2956篇
  2005年   2590篇
  2004年   2114篇
  2003年   1829篇
  2002年   1676篇
  2001年   1410篇
  2000年   1313篇
  1999年   764篇
  1998年   475篇
  1997年   430篇
  1996年   444篇
  1995年   469篇
  1994年   443篇
  1993年   322篇
  1992年   410篇
  1991年   431篇
  1990年   444篇
  1989年   401篇
  1988年   361篇
  1987年   462篇
  1986年   432篇
  1985年   444篇
  1984年   403篇
  1983年   373篇
  1982年   378篇
  1981年   367篇
  1980年   282篇
  1979年   229篇
  1978年   183篇
  1977年   266篇
  1976年   279篇
  1975年   308篇
  1974年   306篇
  1973年   200篇
  1972年   278篇
  1971年   268篇
  1970年   261篇
  1968年   190篇
  1967年   358篇
  1965年   339篇
  1964年   186篇
排序方式: 共有10000条查询结果,搜索用时 218 毫秒
1.
Watermelon peel residues were used to produce a new biochar by dehydration method. The new biochar has undergone two methods of chemical modification and the effect of this chemical modification on its ability to adsorb Cr(VI) ions from aqueous solution has been investigated. Three biochars, Melon-B, Melon-BO-NH_2 and Melon-BO-TETA, were made from watermelon peel via dehydration with 50% sulfuric acid to give Melon-B followed by oxidation with ozone and amination using ammonium hydroxide to give Melon-BO-NH_2 or Triethylenetetramine(TETA) to give Melon-BO-TETA. The prepared biochars were characterized by BET, BJH,SEM, FT-IR, TGA, DSC and EDAX analyses. The highest removal percentage of Cr(VI) ions was 69% for Melon-B,98% for Melon-BO-NH_2 and 99% for Melon-BO-TETA biochars of 100 mg·L~(-1) Cr(VI) ions initial concentration and 1.0 g·L~(-1) adsorbents dose. The unmodified biochar(Melon-B) and modified biochars(Melon-BO-NH_2 and Melon-BO-TETA) had maximum adsorption capacities(Qm) of 72.46, 123.46, and 333.33 mg·g~(-1), respectively.The amination of biochar reduced the pore size of modified biochar, whereas the surface area was enhanced.The obtained data of isotherm models were tested using different error function equations. The Freundlich,Tempkin and Langmuir isotherm models were best fitted to the experimental data of Melon-B, Melon-BO-NH_2 and Melon-BO-TETA, respectively. The adsorption rate was primarily controlled by pseudo-second–order rate model. Conclusively, the functional groups interactions are important for adsorption mechanisms and expected to control the adsorption process. The adsorption for the Melon-B, Melon-BO-NH_2 and Melon-BO-TETA could be explained for acid–base interaction and hydrogen bonding interaction.  相似文献   
2.
3.
Chiral 1,1’-binaphthyl-linked diporphyrin ‘tweezers’ (R)-1/(S)-1 and the corresponding zinc(II) complexes (R)-2/(S)-2 were prepared as chiral host molecules, and their utility for chiral analyses (especially enantiomeric excess (ee) determinations) were evaluated. Tris(1-n-dodecyl)porphyrins were used for the first time as the interacting units. Host capabilities of the diporphyrin tweezers were investigated by titrations with (R,R)- and (S,S)-cyclohexane-1,2-diamine (CHDA). The host molecules could be used as multichannel probes of ee by using UV-vis, circular dichroism (CD), fluorescence emission and 1H nuclear magnetic resonance (1H-NMR) methods. Chiral configurations could also be differentiated using CD or 1H-NMR spectroscopy. All three optical techniques give good resolution of ee with reasonable sensitivity considering the low concentrations used (ca. 10−6 mol·L−1). The ee determination of CHDA enantiomers using NMR spectroscopy is also possible because of the reasonably well separated resonances in the case of (R,R)- and (S,S)-CHDA. Non-metallated (R)-1/(S)-1 hosts could not be used to detect chiral information in a strongly acidic chiral guest. This work demonstrates the utility of 1,1’-binapthyl-linked chiral hosts for chiral analysis of ditopically interacting enantiomers.  相似文献   
4.
A novel microporous two-dimensional(2D)Ni-based phosphonate metal-organic framework(MOF;denoted as IEF-13)has been successfully synthesized by a simple and green hydrothermal method and fully characterized using a combination of experimental and computational techniques.Structure resolution by single-crystal X-ray diffraction reveals that IEF-13 crystallizes in the triclinic space group Pi having bi-octahedra nickel nodes and a photo/electroactive tritopic phosphonate ligand.Remarkably,this material exhibits coordinatively unsaturated nickel(II)sites,free-P03H2and-P03H acidic groups,a C02accessible microporosity,and an exceptional thermal and chemical stability.Further,its in-deep optoelectronic characterization evidences a photoresponse suitable for photocatalysis.In this sense,the photocatalytic activity for challenging H2generation and overall water splitting in absence of any co-catalyst using UV-Vis irradiation and simulated sunlight has been evaluated,constituting the first report for a phosphonate-MOF photocatalyst.IEF-13 is able to produce up to 2,200 fimol of H2per gram using methanol as sacrificial agent,exhibiting stability,maintaining its crystal structure and allowing its recycling.Even more,170μmol of H2per gram were produced using IEF-13 as photocatalyst in the absence of any co-catalyst for the overall water splitting,being this reaction limited by the 02reduction.The present work opens new avenues for further optimization of the photocatalytic activity in this type of multifunctional materials.  相似文献   
5.
Covalent triazine frameworks (CTFs) have been recently employed for visible light-driven photocatalysis due to their unique optical and electronic properties. However, the usually highly hydrophobic nature of CTFs, which originates from their overall aromatic backbone, leads to limitations of CTFs for applications in aqueous media. In this study, we aim to extend the range of the application media of CTFs and design hybrid material of a CTF and mesoporous silica (SBA-15) for efficient photocatalysis in aqueous medium. A thiophene-containing CTF was directly synthesized in mesopores of SBA-15. Due to the high surface area and the added hydrophilic properties by silica, the hybrid material demonstrated excellent adsorption of organic molecules in water. This leads not only to high photocatalytic performance of the hybrid material for the degradation of organic dyes in water, but also for efficient photocatalysis in solvent-free and solid state. Furthermore, the reusability, stability and easy recovery of the hybrid material offers promising metal-free heterogeneous photocatalyst for broader applications in different reaction media.  相似文献   
6.
The concept of“robust dynamics”describes the incorporation of mechanically interlocked molecules(MIMs)into metal-organic framework(MOF)materials such that large amplitude motions(e.g.,rotation or translation of a macrocycle)can occur inside the free volume pore of the MOF.To aid in the preparation of such materials,reticular synthesis was used herein to design rigid molecular building blocks with predetermined ordered structures starting from the well-known MOF NOTT-101.New linkers were synthesized that have a T-shape,based on a triphenylene tetra-carboxylate strut,and their incorporation into Cu(II)-based MOFs was investigated.The single-crystal structures of three new MOFs,UWCM-12(fof),β-UWCM-13(loz),UWCM-14(lil),with naked T-shaped linkers were determined;β-UWCM-13 is the first reported example of the loz topology.A fourth MOF,UWDM-14(lil)is analogous to UWCM-14(lil)but contains a[2]rotaxane linker.Variable-temperature,2H solid-state NMR was used to probe the dynamics of a 24-membered macrocycle threaded onto the MOF skeleton.  相似文献   
7.
我们经常使用Google的图片服务器搜索图片(http://images.google.com/),先输入关键词搜索出一大堆的结果,然后一个一个点击打开再保存图像,非常麻烦。这里推荐大家试试GoogleGrab,它直接将符合你条件的图片下载下来,免去我们逐个打开保存之苦。  相似文献   
8.
1 Introduction High power laser diode arrays (LDA) have many advan- tages such as small volume, long working life, high slope efficiency and high optical density, so they have many applications in medical treatment, material pro- cessing, and for the pumping source of solid laser and etc. But unfortunately, the LDA can not be easy to use directly in these fields because of their poor beam quality and extremely asymmetric divergent beams (!x≈ 5°~10°and !y≈20°~35°, for example), so it …  相似文献   
9.
10.
Physical properties and microstructural evolution on firing of 3 types of bauxite based refractory bricks were carried out using techniques such as porosimetry,XRD and SEM.The groups differed from each other by progressive refining of the matrix or bond phase.It is revealed that such a refinement of the matrix can improve the high temperature properties of the bricks made from poor grade materials.  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-23

京公网安备 11010802026262号