全文获取类型
收费全文 | 5902篇 |
免费 | 502篇 |
国内免费 | 1577篇 |
专业分类
化学 | 5614篇 |
晶体学 | 58篇 |
力学 | 202篇 |
综合类 | 13篇 |
数学 | 53篇 |
物理学 | 2041篇 |
出版年
2024年 | 16篇 |
2023年 | 172篇 |
2022年 | 190篇 |
2021年 | 214篇 |
2020年 | 268篇 |
2019年 | 201篇 |
2018年 | 178篇 |
2017年 | 231篇 |
2016年 | 308篇 |
2015年 | 266篇 |
2014年 | 332篇 |
2013年 | 527篇 |
2012年 | 447篇 |
2011年 | 574篇 |
2010年 | 444篇 |
2009年 | 573篇 |
2008年 | 507篇 |
2007年 | 528篇 |
2006年 | 405篇 |
2005年 | 335篇 |
2004年 | 255篇 |
2003年 | 206篇 |
2002年 | 110篇 |
2001年 | 113篇 |
2000年 | 65篇 |
1999年 | 55篇 |
1998年 | 82篇 |
1997年 | 88篇 |
1996年 | 52篇 |
1995年 | 39篇 |
1994年 | 26篇 |
1993年 | 28篇 |
1992年 | 33篇 |
1991年 | 18篇 |
1990年 | 14篇 |
1989年 | 16篇 |
1988年 | 14篇 |
1987年 | 6篇 |
1986年 | 11篇 |
1985年 | 12篇 |
1983年 | 2篇 |
1982年 | 6篇 |
1981年 | 2篇 |
1976年 | 1篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1971年 | 2篇 |
1970年 | 1篇 |
1968年 | 1篇 |
1967年 | 1篇 |
排序方式: 共有7981条查询结果,搜索用时 15 毫秒
101.
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
102.
Summary The capabilities of sulfur hexafluoride as a mobile phase for supercritical-fluid chromatography are investigated. An evaluation
of its overall utility on the basis of separations of standard aromatic hydrocarbon odel mixtures performed on a variety of
bonded-phase, packed columns with UV detection is presented. The dependence of separation performance upon operational parameters
is also examined. A comparative evaluation of the chroamtographic properties of supercitrical sulfur hexafluoride and those
of supercritical carbon dioxide is developed from these separations under corresponding supercritical state conditions. 相似文献
103.
Cu/TiO2-NiO上光促表面催化CO2和H2O合成CH3OH反应规律 总被引:8,自引:0,他引:8
采用溶胶-凝胶法制备了n(电子型)-p(空穴型) 复合半导体材料0.5%Cu/TiO2-2.0%NiO (w),利用X射线衍射(XRD)、透射电镜(TEM)、红外光谱(IR)、紫外-可见光漫反射(UV-Vis)、程序升温脱附(TPD)技术对材料结构、吸光性能、化学吸附性能进行了表征,研究了该材料对CO2和H2O合成CH3OH的光促表面催化反应(PSSR)规律.结果表明,所制备材料能够明显促进目的反应,室温条件下即有CH3OH生成.在200 ℃下,由于光-表面-热的协同效应,CO2转化率得以提高,且CH3OH的选择性达到87.5% .根据实验结果,得出CO2在材料表面的卧式吸附态为CH3OH的前驱物,并对PSSR机理进行了讨论. 相似文献
104.
105.
Norikazu Nishiyama Yong-Rong Dong Tao Zheng Yasuyuki Egashira Korekazu Ueyama 《Journal of membrane science》2006,280(1-2):603-609
Microporous carbon membranes were prepared on an -alumina support by a pyrolysis of cationic tertiary amine/anionic polymer composites. The precursor solutions contain a thermosetting resorcinol/formaldehyde (RF) polymer and a cationic tertiary amine. Three types of cationic tertiary amines with different chain lengths were used, such as tetramethlammonium bromide (TMAB), tetrapropylammonium bromide (TPAB) and cetyltrimethylammonium bromide (CTAB). A porous structure was produced by a decomposition of the amine and the resulting pores assisted the further gasification of the RF polymer at high temperature. The carbon/alumina membranes have thin and continuous carbon top layers with a thickness of 1 μm. Gas permeation tests were performed using single gases of CO2, O2, N2, CF4, n-C4H10 and i-C4H10, as well as binary mixtures of CH4/n-C4H10 and N2/CF4 at different temperatures between 23 and 150 °C. The carbon membrane prepared using TMAB showed separation factors higher than 650 for the CH4/n-C4H10 mixtures and higher than 8100 for the N2/CF4 mixture. From the permeation of pure gases with different molecular sizes, the pore sizes of the carbon membrane prepared using TMAB, TPAB and CTAB are estimated to be 4.0, 5.0 and larger than 5.5 Å, respectively, indicating that the micropore size of the carbon membranes is controllable by using different amines. 相似文献
106.
A procedure of analysis for small-angle X-ray scattering (SAXS) data has been established to obtain density fluctuation of supercritical fluids near the critical point. It is indispensable for the certain analysis to utilize both of high-quality SAXS data measured under stable thermodynamic condition and accurate P–ρ–T data in supercritical region. As a standard example, SAXS measurements have been performed for supercritical CO2, which is a suitable sample satisfying the condition for both experiment and analysis. The measurements were carried out along four isothermal conditions at reduced temperature of Tr = T/Tc = 1.020, 1.022, 1.043 and 1.064. Comparing the experimental density fluctuation with calculated one from the most reliable equation of state, the differences are within 8% at most. 相似文献
107.
Conduction stability of high-density polyethylene/carbon black (HDPE/CB) composites with a CB volume fraction slightly above the percolation threshold is studied in relation to electric field action at various ambient temperatures below the melting point of HDPE. It is found that resistance of the composites shows considerable changes after the electric field is switched off. Influence of irradiation crosslinking of HDPE on the conduction stability is also discussed. 相似文献
108.
对铝原子簇Al_n(n=1~10,12,13)已报导过的理论预测几何构型进行合理选择, 用量子化学CNDO/2法研究了单分子一氧化碳在这些簇上取不同吸附位形时的吸附作用。结果表明吸附强度随簇尺度的变化呈“幻数”特性: Al_2、Al_6、Al_(12)簇具有特别高的吸附能, 与实验观测结果相符。采用作者建议的推广电子壳模型可合理解释这一尺度效应。对Al_(12)和Al_(13)簇电子结构的分析进一步支持了壳模型的观点。随着簇的增大, 尺度效应逐步减弱并趋向于体相铝的性质。 相似文献
109.
《Electroanalysis》2005,17(1):79-84
Fabrication, electrochemical characterization, and applications of low‐site density carbon nanotubes based nanoelectrode arrays (CNTs‐NEAs) are reported in this work. Spin‐coating of an epoxy resin provides a new way to create the electrode passivation layer effectively reducing electrode capacitance and current leakage. Cyclic voltammetry showed the sigmoidal shape curves with low capacitive current and scan‐rate‐independent limiting current. Square‐wave voltammetry showed well‐defined peak shapes in voltammograms of K3Fe(CN)6 and 4‐acetamidophenol (acetaminophen) and the peak currents to be proportioned to their concentrations, demonstrating the feasibility for voltammetric analysis of the CNTs‐NEAs. The CNTs‐NEAs were also used successfully for voltammetric detection of trace concentrations of lead(II) at ppb level at first‐time. The CNTs‐NEAs provide an excellent platform for ultra sensitive electrochemical sensors for chemical and biological sensing. 相似文献
110.
Published data on silicon carbide nanotubes (SiC-NT) are analyzed. According to theoretical calculations, single-layer SiC-NTs
do not dissociate, but they have not yet been detected experimentally. According to the experimental data, metastable SiC-NTs
with walls consisting of several layers and nanotube fibers were produced. The optimized structure of single-layer SiC-NTs
was calculated by the RHF/6-31G quantum-chemical method. The possibility of obtaining SiC-NTs by gas-phase chemical deposition
from methyltrichlorosilane in the temperature range of 800–1000 °C was investigated. Nanofibers and polygrained SiC nanotubes
were obtained, but ordinary layer SiC nanotubes were not detected. To remove the inconsistencies it was first proposed to
classify the nanotubes according to the structure of their walls, separating all the SiC-NTs into three types: 1) ordinary
layer nanotubes with rolled layers, similar to carbon nanotubes; 2) polynanocrystalline nanotubular fibers or nanotubes with
walls consisting of linked differently oriented nanograins; 3) monocrystalline synthetic nanotubes with ideal crystalline
walls. It was concluded that the ordinary SiC-NTs of the first type are unstable with the exception of one-or two-layer nanotubes;
stable SiC-NTs of the first type and SiC-NTs of the third type have not yet been discovered; only nanotubular fibers of the
second type were obtained experimentally.
__________
Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 1, pp. 3–13, January–February, 2006. 相似文献