全文获取类型
收费全文 | 769篇 |
免费 | 30篇 |
国内免费 | 248篇 |
专业分类
化学 | 896篇 |
晶体学 | 7篇 |
力学 | 8篇 |
物理学 | 136篇 |
出版年
2024年 | 1篇 |
2023年 | 18篇 |
2022年 | 15篇 |
2021年 | 29篇 |
2020年 | 26篇 |
2019年 | 31篇 |
2018年 | 32篇 |
2017年 | 23篇 |
2016年 | 37篇 |
2015年 | 52篇 |
2014年 | 40篇 |
2013年 | 42篇 |
2012年 | 43篇 |
2011年 | 82篇 |
2010年 | 84篇 |
2009年 | 94篇 |
2008年 | 78篇 |
2007年 | 77篇 |
2006年 | 61篇 |
2005年 | 46篇 |
2004年 | 35篇 |
2003年 | 22篇 |
2002年 | 20篇 |
2001年 | 17篇 |
2000年 | 12篇 |
1999年 | 10篇 |
1998年 | 5篇 |
1997年 | 4篇 |
1996年 | 3篇 |
1995年 | 2篇 |
1994年 | 1篇 |
1990年 | 5篇 |
排序方式: 共有1047条查询结果,搜索用时 15 毫秒
41.
Using the self-assembly β-cyclodextrin (β-CD) and cetyltrimethylammonium bromide (CTAB) as structure-directing agents, high-quality ordered MCM-41 silicas have been prepared. Small-angle X-ray diffraction (SXRD), N2 adsorption-desorption and scanning electron microscope (SEM) techniques were used to characterize the calcined samples. Results showed that the pore structure of the resulting mesoporous silica belonged to the two-dimensional hexagonal structure (space group p6mm). The high-quality hexagonal structure was formed as n?1 (n denotes molar ratio of β-CD to CTAB). N2 adsorption-desorption curves revealed type IV isotherms, H4 hysteresis loops, for all samples, and H1 hysteresis loops for samples at n=0, 0.1, 1 and 2, respectively. The pore size and the pore wall thickness of the samples increased with the increase in n values, respectively. 相似文献
42.
Pierre Braunstein 《Journal of organometallic chemistry》2004,689(24):3953-3967
In this account, we focus on results from our laboratory to illustrate recent developments in various fields of organometallic chemistry. Studies on hemilabile P,N donor ligands and on the ion-pair behaviour of cationic Pd(II) complexes have led to the full characterization of complexes with η1-allyl ligands. This still rare bonding mode for the allyl ligand in palladium chemistry allows facile insertion of CO into the Pd-C σ-bond, in contrast to the situation in related η3-allyl Pd(II) complexes. In order to develop new homogeneous catalysts for the selective dimerization and oligomerization of ethylene, a range of Ni(II) complexes have been prepared with new chelating P,N ligands where P represents a phosphine, phosphinite or phosphonite donor group and N a pyridine or oxazoline moiety. Finally, we shall examine bottom-up approaches to the formation of new nanomaterials of magnetic or catalytic interest by covalent anchoring of metal complexes and clusters into mesoporous materials using functional phosphine or alkyne ligands containing an alkoxysilyl group. 相似文献
43.
Synthesis of functionalized mesoporous carbon by an easy-accessed method is of great importance towards its practical applications.Herein,an evaporation induced self-assembly/carbonization(EISAC) method was developed and applied to the synthesis of sulfonic acid group functionalized mesoporous carbon(SMC).The final mesoporous carbon obtained by EISAC method possesses wormlike mesoporous structure,uniform pore size(3.6 nm),large surface area of 735 m2/g,graphitic pore walls and rich sulfonic acid group.Moreover,the resultant mesoporous carbon achieves a superior electrochemical capacitive performances(216 F/g)to phenolic resin derived mesoporous carbon(OMC,152 F/g)and commercial activated carbon(AC,119 F/g). 相似文献
44.
This review discusses the latest advances in electrodeposition of nanostructured catalysts for electrochemical energy conversion: fuel cells, water splitting, and carbon dioxide electroreduction. The method excels at preparing efficient and durable nanostructured materials, such as nanoparticles, single atom clusters, hierarchical bifunctional combinations of hydroxides, selenides, phosphides, and so on. Yet, in most cases, chemical composition cannot be decoupled from catalyst morphology. This compromises the rational design of electrodeposition procedures because performance indicators depend on both morphology and surface chemistry. We expect electrodeposition will keep unraveling its potential as the preferred method for electrocatalyst synthesis once a deeper understanding of the electrochemical growth process is combined with complex chemistries to have control of the morphology and the surface composition of complex (bifunctional) electrocatalysts. 相似文献
45.
Stabilized mesoporous TiO2 was synthesized by evaporation induced self assembly (EISA) method and mechanically incorporated into single-walled carbon nanotubes (SWCNT) with different ratios. The physicochemical properties of the nanocomposites (mesoporous TiO2/SWCNT) materials were investigated by Brunauer–Emmett–Teller (BET) measurement, X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive X-ray (EDX), photoluminescence (PL) and ultraviolet–visible (UV–Vis) spectroscopy measurements. The catalytic activity of mesoporous TiO2 and nanocomposites were assessed by examining the degradation of rhodamine B as model aqueous solution under visible light. CNTs are facilitating the photocatalytic activity of mesoporous TiO2 in the degradation of rhodamine B efficiently. 相似文献
46.
Hierarchical flower-like architectures of[Ni3(BTC)2·12H2O](BTC3=benzene-1,3,5-tricarboxylate) were successfully prepared by a simple solution-phase method under mild conditions without any template or surfactant.Phase-pure porous NiO nanocrystals were obtained by annealing the Ni-BTC complex without significant alteration in morphology.The product was characterized by X-ray diffraction techniques,field-emission scanning electron microscopy(FESEM).transmission electron microscopy(TEM) and high-resolution TEM(HRTEM).The catalytic effect of the NiO product was investigated on the thermal decomposition of ammonium perchlorate(AP) and it was found that the annealed NiO product has higher catalytic activity than the commercial NiO. 相似文献
47.
Hankun Zhou Si Chen Ning Gan Tianhua Li Yuting Cao Qianli Jiang 《Electroanalysis》2013,25(10):2384-2393
A novel sandwich‐type electrochemiluminescence (ECL) immunosensor was developed to enable the sensitive detection of HIV‐1 antibodies. This system incorporated mesoporous silica (mSiO2) complexed with quantum dots (QDs) and nano‐gold particles, which were assembled to enhance signal detection. Magnetic beads were used by immobilizing the secondary anti‐IgG antibody. This was first employed to capture HIV‐1 antibody (Ab) to form a Fe3O4/anti‐IgG/Ab complex. A high loading and signal‐enhanced nanocomposite (hereafter referred to as Au‐mSiO2‐CdTe) was used as a HIV‐1 antigen label. The Au‐mSiO2‐CdTe nanocomposite was conjugated with the Fe3O4/anti‐IgG/Ab complex to form an immunocomplex (hereafter referred to as Fe3O4/anti‐IgG/Ab/HIV‐1/CdTe‐mSiO2‐Au). This complex could be further separated by an external magnetic field to produce ECL signals. Due to the large specific surface area and pore volume of mSiO2, the loading of the CdTe QDs was markedly increased. Thus, the loaded QDs released a powerful chemiluminescent signal with a concordantly increased sensitivity of the immunosensor. The immunosensor was highly sensitive, and displayed a linear range of responses for HIV‐1 antibody across a dilution range of 1 : 1500 through 1 : 50 with the detection limit of 1 : 4500. The immunoassay can be a promising candidate in early diagnosis of HIV infection. 相似文献
48.
Chariklia Sotiriou-Leventis Xiaojiang Wang Sudhir Mulik Arumugam Thangavel Nicholas Leventis 《合成通讯》2013,43(14):2285-2298
Immobilization of catalysts on solid supports is a promising approach to combine the advantages of heterogeneous and homogeneous catalysts. Pd(PPh3)2Cl2, known as an extremely active homogeneous catalyst for the Sonogashira coupling reaction, has been immobilized on high-surface-area MCF (mesocellular foams)–type mesoporous silica powder modified with 3-aminopropyltriethoxysilane and subsequently with diphenylphosphine. The functionalized MCF-type silica and supported catalysts have been characterized by x-ray photoelectron spectroscopy (XPS), fourier transform infrared spectroscopy (FTIR), elemental analysis, nitrogen sorption porosimetry, and scanning electron microscopy (SEM). Such supported Pd catalysts have proven to be useful recyclable reagents for copper- and amine-free Sonogashira coupling reactions of haloaromatic compounds with terminal alkynes. 相似文献
49.
AbstractAmino-functionalized mesoporous silica nanoparticles (AFMSN) were prepared based on the self-assembly process of the pre-fabricated template of anionic gemini surfactant. The perfect mass ration of the reactants for the synthesis of the AFMSN with high surface area and amino loading was optimized by orthogonal experiments. Adsorption capability of the optimized product for lead ion (Pb2+) was investigated in detail. Specially, the effects of the amino content, solution pH, adsorbent dosage, temperature, and interference of other metal ions on the removal efficiency of Pb2+ were studied. It is found that these factors can greatly affect the removal efficiency of Pb2+ and the prepared adsorbent exhibits the high adsorption selectivity for Pb2+. At an optimal condition, the AFMSN adsorbent presents an excellent adsorption capacity for Pb2+ up to 211.42?mg/g. The adsorption kinetics study revealed that the pseudo-second-order model could well describe the Pb2+ adsorption process, and the adsorption isotherm was fitted well with the Langmuir model. More importantly, the AFMSN adsorbent could be recycled 8 times and a high adsorption efficiency of Pb2+ could still be maintained. Therefore, the prepared AFMSN adsorbent may find practical application in removing Pb2+ from the polluted water. 相似文献
50.
The pure silica mesoporous molecular sieve MCM‐41 was synthesized under hydrothermal conditions. Pd/Si‐MCM‐41 was prepared by the incipient wetness impregnation of pure silica MCM‐41 with mixed solution of PdCl2, ethanol and CH2Cl2. The samples were characterized by x‐ray diffraction (XRD), transmission electron microscopy (TEM), and nitrogen adsorption–desorption isotherms at 77 K. The XRD and TEM results reveal that Pd is actually anchored inside the pores of Si‐MCM‐41 and the Si‐MCM‐41 structure is clearly maintained after impregnation. 相似文献