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   2915篇
  免费   676篇
  国内免费   88篇
化学   3052篇
晶体学   47篇
力学   6篇
综合类   2篇
数学   7篇
物理学   565篇
  2024年   1篇
  2023年   10篇
  2022年   16篇
  2021年   61篇
  2020年   150篇
  2019年   115篇
  2018年   69篇
  2017年   78篇
  2016年   186篇
  2015年   212篇
  2014年   231篇
  2013年   269篇
  2012年   252篇
  2011年   218篇
  2010年   251篇
  2009年   243篇
  2008年   252篇
  2007年   234篇
  2006年   224篇
  2005年   168篇
  2004年   160篇
  2003年   125篇
  2002年   24篇
  2001年   31篇
  2000年   21篇
  1999年   22篇
  1998年   14篇
  1997年   21篇
  1996年   10篇
  1995年   3篇
  1993年   1篇
  1991年   1篇
  1990年   4篇
  1985年   1篇
  1984年   1篇
排序方式: 共有3679条查询结果,搜索用时 390 毫秒
131.
Carbon quantum dots (CQDs) were synthesized by heating various carbon sources in HNO3 solution at reflux, and the effects of HNO3 concentration on the size of the CQDs were investigated. Furthermore, the oxygen‐containing surface groups of as‐prepared CQDs were selectively reduced by NaBH4, leading to new surface states. The experimental results show that the sizes of CQDs can be tuned by HNO3 concentration and then influence their photoluminescent behaviors; the photoluminescent properties are related to both the size and surface state of the CQDs, but the photocatalytic activities are determined by surface states alone. The different oxygen‐containing groups on the surface of the CQDs can induce different degrees of the band bending upward, which determine the separation and combination of the electron–hole pairs. The high upward band bending, which is induced by C?O and COOH groups, facilitates separation of the electron–hole pairs and then enhances high photocatalytic activity. In contrast, the low upward band bending induced by C? OH groups hardly prevents the electron–hole pairs from surface recombination and then exhibits strong photoluminescence. Therefore, both the photocatalytic activities and optical properties of CQDs can be tuned by their surface states.  相似文献   
132.
Core–shell‐structured mesoporous silica spheres were prepared by using n‐octadecyltrimethoxysilane (C18TMS) as the surfactant. Hollow mesoporous carbon spheres with controllable diameters were fabricated from core–shell‐structured mesoporous silica sphere templates by chemical vapor deposition (CVD). By controlling the thickness of the silica shell, hollow carbon spheres (HCSs) with different diameters can be obtained. The use of ethylene as the carbon precursor in the CVD process produces the materials in a single step without the need to remove the surfactant. The mechanism of formation and the role played by the surfactant, C18TMS, are investigated. The materials have large potential in double‐layer supercapacitors, and their electrochemical properties were determined. HCSs with thicker mesoporous shells possess a larger surface area, which in turn increases their electrochemical capacitance. The samples prepared at a lower temperature also exhibit increased capacitance as a result of the Brunauer–Emmett–Teller (BET) area and larger pore size.  相似文献   
133.
A solvothermal post‐treatment method was developed to synthesize Fe3O4@mesosilica core–shell nanospheres (CSNs) with a well‐preserved morphology, mesoporous structure, and tunable large pore diameters (2.5–17.6 nm) for the first time. N,N‐Dimethylhexadecylamine (DMHA), which was generated in situ during the heat‐treatment process, was mainly responsible for this pore‐size enlargement, as characterized by NMR spectroscopy. This pore‐size expansion can be strengthened with the aid of hexamethyldisilazane (HMDS), whilst the nature of the surface of the Fe3O4@mesosilica CSNs can be easily modified with trimethylsilyl groups during the pore‐size‐expansion process. The hydrophobicity of the Fe3O4@mesosilica CSNs increased for the enlarged mesopores and the adsorption capacity of these CSNs for benzene (up to 1.5 g g?1) is the highest ever reported for Fe3O4@mesosilica CSNs. The resultant Fe3O4@mesosilica CSNs (pore size: 10 nm) showed a 3.6‐times higher adsorption capacity of lysozyme than those without the pore expansion (pore size: 2.5 nm), thus making them a good candidate for loading large molecules.  相似文献   
134.
135.
In this study, surface‐functionalized, branched polyethylenimine (BPEI)‐modified YVO4:Bi3+,Eu3+ nanocrystals (NCs) were successfully synthesized by a simple, rapid, solvent‐free hydrothermal method. The BPEI‐coated YVO4:Bi3+,Eu3+ NCs with high crystallinity show broad‐band excitation in the λ=250 to 400 nm near‐ultraviolet (NUV) region and exhibit a sharp‐line emission band centered at λ=619 nm under excitation at λ=350 nm. The surface amino groups contributed by the capping agent, BPEI, not only improve the dispersibility and water/buffer stability of the BPEI‐coated YVO4:Bi3+,Eu3+ NCs, but also provide a capability for specifically targeted biomolecule conjugation. Folic acid (FA) and epidermal growth factor (EGF) were further attached to the BPEI‐coated YVO4:Bi3+,Eu3+ NCs and exhibited effective positioning of fluorescent NCs toward the targeted folate receptor overexpressed in HeLa cells or EGFR overexpressed in A431 cells with low cytotoxicity. These results demonstrate that the ligand‐functionalized, BPEI‐coated YVO4:Bi3+, Eu3+ NCs show great potential as a new‐generation biological luminescent bioprobe for bioimaging applications. Moreover, the unique luminescence properties of BPEI‐coated YVO4:Bi3+,Eu3+ NCs show potential to combine with a UVA photosensitizing drug to produce both detective and therapeutic effects for human skin cancer therapy.  相似文献   
136.
Celecoxib belongs to a new NSAID family specifically inhibiting cyclooxygenase‐2 (COX‐2). The present formulations require high dosage since the transmembrane transport fluctuates and is very difficult to control. We solubilized celecoxib in micelles of nonionic microemulsions and hydrophilic surfactant. The supersaturated solubilized drug was precipitated from the nano‐droplets to form a new solid structure with improved dissolution properties. The selected microemulsion systems loaded with celecoxib were characterized by SAXS, SD‐NMR, viscosity, and electrical conductivity techniques. Precipitation was conducted from W/O as well as from O/W U‐type microemulsions. The crystals obtained by the precipitation were characterized by x‐ray powder scattering, differential scanning calorimetry, FTIR measurements, and microscopic scans.  相似文献   
137.
A novel ozone (O3) sensor is fabricated using commercial metal oxide field effect transistor (MOSFET), modified with single-walled carbon nanotubes (SWCNTs). In this study, integrated circuit (IC: BS250) was selected as the selective probe for O3 detection. For this purpose, a plastic cover on the surface of the drain was drilled to bare the drain surface, followed by its modification with nitrogen and sulfur-functionalized SWCNTs by chemical vapor deposition (CVD) process. The CVD-synthesized SWCNTs were then electrodeposited with FeOOH nanostructures. According to the figures of merit, the fabricated sensor gave a linear output from 20 to 450 parts per billion (ppb). Detection limit was also 4.1?ppb. Relative standard deviation (RSD) for seven replicate analyses was 3.61%. Based on 90% of maximum response (t90), the response time was ~1.5?min. Calibration sensitivity was measured to 1.3?mV/ppb. No interference was observed, when introducing at least 500 folds of interferences of gaseous species such as H2O, HCl, H2S, O2, H2, CO, CO2, NO2, SO2, Cl2, C2H2, CH4 and volatile organic compounds (VOCs) to 250?ppb of O3 solution. Reliability of the sensor was also evaluated via determination of O3 in different air samples.  相似文献   
138.
A facile and efficient strategy for the synthesis of hierarchical yolk–shell microspheres with magnetic Fe3O4 cores and dielectric TiO2 shells has been developed. Various Fe3O4@TiO2 yolk–shell microspheres with different core sizes, interstitial void volumes, and shell thicknesses have been successfully synthesized by controlling the synthetic parameters. Moreover, the microwave absorption properties of these yolk–shell microspheres, such as the complex permittivity and permeability, were investigated. The electromagnetic data demonstrate that the as‐synthesized Fe3O4@TiO2 yolk–shell microspheres exhibit significantly enhanced microwave absorption properties compared with pure Fe3O4 and our previously reported Fe3O4@TiO2 core–shell microspheres, which may result from the unique yolk–shell structure with a large surface area and high porosity, as well as synergistic effects between the functional Fe3O4 cores and TiO2 shells.  相似文献   
139.
A three‐dimensional (3D) hierarchical carbon–sulfur nanocomposite that is useful as a high‐performance cathode for rechargeable lithium–sulfur batteries is reported. The 3D hierarchically ordered porous carbon (HOPC) with mesoporous walls and interconnected macropores was prepared by in situ self‐assembly of colloidal polymer and silica spheres with sucrose as the carbon source. The obtained porous carbon possesses a large specific surface area and pore volume with narrow mesopore size distribution, and acts as a host and conducting framework to contain highly dispersed elemental sulfur. Electrochemical tests reveal that the HOPC/S nanocomposite with well‐defined nanostructure delivers a high initial specific capacity up to 1193 mAh g?1 and a stable capacity of 884 mAh g?1 after 50 cycles at 0.1 C. In addition, the HOPC/S nanocomposite exhibits high reversible capacity at high rates. The excellent electrochemical performance is attributed exclusively to the beneficial integration of the mesopores for the electrochemical reaction and macropores for ion transport. The mesoporous walls of the HOPC act as solvent‐restricted reactors for the redox reaction of sulfur and aid in suppressing the diffusion of polysulfide species into the electrolyte. The “open” ordered interconnected macropores and windows facilitate transportation of electrolyte and solvated lithium ions during the charge/discharge process. These results show that nanostructured carbon with hierarchical pore distribution could be a promising scaffold for encapsulating sulfur to approach high specific capacity and energy density with long cycling performance.  相似文献   
140.
The structures of three newly synthesized phosphonate‐substituted polyoxotitanates are reported. The Ti/O core of [Ti4O(OEt)12(PhenylPO3)] ( 1 ) is the building block for two larger phosphonate‐substituted nanoclusters, [Ti25O26(OEt)36(PhenylPO3)6] ( 2 ) and [Ti26O26(OEt)39(PhenylPO3)6]Br ( 3 ). All compounds exhibit a not previously recognized triply bridging binding mode of the phosphonate anchor with short connecting Ti? O bonds, the average of which is 2.010(7) Å. Comparison with previously reported work suggests that the binding mode of the phosphonate anchor is strongly dependent on the structure of the underlying substrate.  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