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   11462篇
  免费   2223篇
  国内免费   2756篇
化学   12572篇
晶体学   232篇
力学   346篇
综合类   67篇
数学   199篇
物理学   3025篇
  2024年   20篇
  2023年   204篇
  2022年   398篇
  2021年   529篇
  2020年   788篇
  2019年   581篇
  2018年   517篇
  2017年   587篇
  2016年   754篇
  2015年   699篇
  2014年   773篇
  2013年   1356篇
  2012年   920篇
  2011年   934篇
  2010年   779篇
  2009年   783篇
  2008年   775篇
  2007年   747篇
  2006年   657篇
  2005年   591篇
  2004年   582篇
  2003年   473篇
  2002年   344篇
  2001年   294篇
  2000年   216篇
  1999年   185篇
  1998年   169篇
  1997年   142篇
  1996年   109篇
  1995年   120篇
  1994年   84篇
  1993年   92篇
  1992年   36篇
  1991年   37篇
  1990年   35篇
  1989年   16篇
  1988年   19篇
  1987年   16篇
  1986年   11篇
  1985年   12篇
  1984年   11篇
  1983年   10篇
  1982年   7篇
  1981年   7篇
  1980年   5篇
  1979年   10篇
  1976年   2篇
  1972年   1篇
  1971年   1篇
  1968年   1篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
91.
Increased concern over the risk resorcinol (RS) pose to ecology and humans, led to its position in European Union Category 1 list of endocrine disruptors. Legal measures restricted RS utilization and hence crucial to monitor its levels in the environment. Herein we report development of highly efficient and economically viable electrochemical sensor for quantitative determination of RS based on 77Maghemite/MultiWall Carbon Nanotube (M/MWCNT) modified carbon paste electrode. M/MWCNT was synthesized via strategic IR irradiation for the first time, a promising approach to overcome other complicated chemical routes. Powder X‐ray diffraction (PXRD), Transmission electron microscopy (TEM), Field emission scanning electron microscopy (FESEM) and Energy dispersive X‐ray (EDX) were used for characterization. Using Differential Pulse Voltammetry (DPV), we report the lowest detection limit at 0.02 μM. The potential application of the sensor was accomplished as a result of excellent recoveries made from real samples fortified with RS. Results indicated the proficiency of the sensor reliable for rapid, onsite monitoring of RS water contamination and in biological matrices.  相似文献   
92.
Carbon dots (CDs), as an emerging fluorescent nanomaterial with low toxicity, has been widely applied in various bio‐related fields. However, investigations on their capabilities in guiding osteogenic differentiation are rarely seen, which has great significance in osteoporosis therapy and bone regeneration. Herein, for the first time, a new kind of Mg2+‐doped CDs is facilely synthesized through a one‐step hydrothermal method from metal gluconate salts. The CDs can serve as nanocarrier of Mg2+ ions entering into cells, and the bioessential metal ions subsequently stimulate osteoblastic differentiation by improving alkaline phosphatase (ALP) activity and upregulation related mRNA expression. Noteworthy, the raw material has almost negligible performance on osteoblastic differentiation compared to Mg‐CDs, which is due to the ultrasmall sizes of CDs and the efficient uptake by cells. Moreover, benefitting from the fluorescence properties, Mg‐CDs can also be applied as cell labeling agents. This work proposes a new strategy to synthesize multifunctional metal ion‐doped CDs, which might had great potential in serving as promising nanodrugs for bone loss therapy.  相似文献   
93.
Sodium/potassium-ion batteries (SIBs/PIBs) arouse intensive interest on account of the natural abundance of sodium/potassium resources, the competitive cost and appropriate redox potential. Nevertheless, the huge challenge for SIBs/PIBs lies in the scarcity of an anode material with high capacity and stable structure, which are capable of accommodating large-size ions during cycling. Furthermore, using sustainable natural biomass to fabricate electrodes for energy storage applications is a hot topic. Herein, an ultra-small few-layer nanostructured MoSe2 embedded on N, P co-doped bio-carbon is reported, which is synthesized by using chlorella as the adsorbent and precursor. As a consequence, the MoSe2/NP-C-2 composite represents exceedingly impressive electrochemical performance for both sodium-ion batteries (SIBs) and potassium-ion batteries (PIBs). It displays a promising reversible capacity (523 mAh g−1 at 100 mA g−1 after 100 cycles) and impressive long-term cycling performance (192 mAh g−1 at 5 A g−1 even after 1000 cycles) in SIBs, which are some of the best properties of MoSe2-based anode materials for SIBs to date. To further probe the great potential applications, full SIBs pairing the MoSe2/NP-C-2 composite anode with a Na3V2(PO4)3 cathode also exhibits a satisfactory capacity of 215 mAh g−1 at 500 mA g−1 after 100 cycles. Moreover, it also delivers a decent reversible capacity of 131 mAh g−1 at 1 A g−1 even after 250 cycles for PIBs.  相似文献   
94.
Three CoII octaazacryptates, with different substituents on the aromatic rings (Br, NO2, CCH), were synthesised and characterised. These and the already published non-substituted cryptate catalysed CO2 photoreduction to CO and CH4 under blue visible light at room temperature. Although CO was observed after short irradiation times and a large range of catalyst concentrations, CH4 was only observed after longer irradiation periods, such as 30 h, but with a small catalyst concentration (25 nm ). Experiments with 13C labelled CO2 showed that CO is formed and reacts further when the reaction time is long. The CCH catalyst is deactivated faster than the others and the more efficient catalyst for CH4 production is the one with Br. This reactivity trend was explained by an energy decomposition analysis based on DFT calculations.  相似文献   
95.
The activation of CS2 is of interest in a broad range of fields and, more particularly, in the context of creating new C−C bonds. The reaction of the dinuclear ytterbium(II) complex [Yb2L4], 1 , [L=(OtBu)3SiO] with carbon disulfide led to the isolation of unprecedented reduction products. In particular, the crystallographic characterization of complex [Yb2L4(μ-C2S2)], 2 , provided the first example of an acetylenedithiolate ligand formed from metal reduction of CS2. Computational studies indicated that this unprecedented reactivity can be ascribed to the unusual binding mode of CS22− in the isolated “key intermediate” [Yb2L4(μ-CS2)], 3 , which results from the dinuclear nature of 1 .  相似文献   
96.
Molybdenum carbide (Mo2C) is a promising noble-metal-free electrocatalyst for the hydrogen evolution reaction (HER), due to its structural and electronic merits, such as high conductivity, metallic band states and wide pH applicability. Here, a simple CVD process was developed for synthesis of a Mo2C on carbon cloth (Mo2C@CC) electrode with carbon cloth as carbon source and MoO3 as the Mo precursor. XRD, Raman, XPS and SEM results of Mo2C@CC with different amounts of MoO3 and growth temperatures suggested a two-step synthetic mechanism, and porous Mo2C nanostructures were obtained on carbon cloth with 50 mg MoO3 at 850 °C (Mo2C-850(50)). With the merits of unique porous nanostructures, a low overpotential of 72 mV at current density of 10 mA cm−2 and a small Tafel slope of 52.8 mV dec−1 was achieved for Mo2C-850(50) in 1.0 m KOH. The dual role of carbon cloth as electrode and carbon source resulted into intimate adhesion of Mo2C on carbon cloth, offering fast electron transfer at the interface. Cyclic voltammetry measurements for 5000 cycles revealed that Mo2C@CC had excellent electrochemical stability. This work provides a novel strategy for synthesizing Mo2C and other efficient carbide electrocatalysts for HER and other applications, such as supercapacitors and lithium-ion batteries.  相似文献   
97.
Enrichment of UVI is an urgent project for nuclear energy development. Herein, magnetic graphitic carbon nitride nanosheets were successfully prepared by in situ anchoring of pyrrhotite (Fe7S8) on the graphitic carbon nitride nanosheet (CNNS), which were used for capturing UVI. The structural characterizations of Fe7S8/CNNS-1 indicated that the CNNS could prevent the aggregation of Fe7S8 and the saturation magnetization was 4.69 emu g−1, which meant that it was easy to separate the adsorbent from the solution. Adsorption experiments were performed to investigate the sorption properties. The results disclosed that the sorption data conformed to the Langmuir isotherm model with the maximum adsorption capacity of 572.78 mg g−1 at 298 K. The results of X-ray photoelectron spectroscopy (XPS) demonstrated that the main adsorption mechanism are as follows: UVI is adsorbed on the surface of Fe7S8/CNNS-1 through surface complexation initially, then it was reduced to insoluble UIV. Thereby, this work provided an efficient and easy to handle sorbent material for extraction of UVI.  相似文献   
98.
Carbon nanotubes (CNTs) are one of the most extensively studied nanomaterials in the 21st century. Since their discovery in 1991, many studies have been reported advancing our knowledge in terms of their structure, properties, synthesis, and applications. CNTs exhibit unique electrothermal and conductive properties which, combined with their mechanical strength, have led to tremendous attention of CNTs as a nanoscale material in the past two decades. To introduce the various types of CNTs, we first provide basic information on their structure followed by some intriguing properties and a brief overview of synthesis methods. Although impressive advances have been demonstrated with CNTs, critical applications require purification, positioning, and separation to yield desired properties and functional elements. Here, we review a versatile technique to manipulate CNTs based on their dielectric properties, namely dielectrophoresis (DEP). A detailed discussion on the DEP aspects of CNTs including the theory and various technical microfluidic realizations is provided. Various advancements in DEP-based manipulations of single-walled and multiwalled CNTs are also discussed with special emphasis on applications involving separation, purification, sensing, and nanofabrication.  相似文献   
99.
100.
We describe the ultrasonic assisted preparation of barium stannate-graphitic carbon nitride nanocomposite (BSO-gCN) by a simple method and its application in electrochemical detection of 4-nitrophenol via electro-oxidation. A bath type ultrasonic cleaner with ultrasonic power and ultrasonic frequency of 100 W and 50 Hz, respectively, was used for the synthesis of BSO-gCN nanocomposite material. The prepared BSO-gCN nanocomposite was characterized by employing several spectroscopic and microscopic techniques such as X-ray diffraction, X-ray photoelectron spectroscopy, fourier transform infra-red, field emission scanning electron microscopy, and high resolution transmission electron microscopy, to unravel the structural and electronic features of the prepared nanocomposite. The BSO-gCN was drop-casted on a pre-treated glassy carbon electrode (GCE), and their sensor electrode was utilized for electrochemical sensing of 4-nitrophenol (4-NP). The BSO-gCN modified GCE exhibited better electrochemical sensing behavior than the bare GCE and other investigated electrodes. The electroanalytical parameters such as charge transfer coefficient (α = 0.5), the rate constant for electron transfer (ks = 1.16 s−1) and number of electron transferred were calculated. Linear sweep voltammetry (LSV) exhibited increase in peak current linearly with 4-NP concentration in the range between 1.6 and 50 μM. The lowest detection limit (LoD) was calculated to be 1 μM and sensitivity of 0.81 μA μM−1 cm−2. A 100-fold excess of various ions, such as Ca2+, Na+, K+, Cl, I, CO32−, NO3, NH4+ and SO42− did not able to interfere with the determination of 4-NP and high sensitivity for detecting 4-NP in real samples was achieved. This newly developed BSO-gCN could be a potential candidate for electrochemical sensor applications.  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