全文获取类型
收费全文 | 797篇 |
免费 | 313篇 |
国内免费 | 218篇 |
专业分类
化学 | 887篇 |
晶体学 | 45篇 |
综合类 | 9篇 |
物理学 | 387篇 |
出版年
2024年 | 18篇 |
2023年 | 31篇 |
2022年 | 87篇 |
2021年 | 97篇 |
2020年 | 124篇 |
2019年 | 72篇 |
2018年 | 74篇 |
2017年 | 48篇 |
2016年 | 82篇 |
2015年 | 52篇 |
2014年 | 33篇 |
2013年 | 63篇 |
2012年 | 40篇 |
2011年 | 47篇 |
2010年 | 42篇 |
2009年 | 54篇 |
2008年 | 47篇 |
2007年 | 43篇 |
2006年 | 46篇 |
2005年 | 48篇 |
2004年 | 34篇 |
2003年 | 36篇 |
2002年 | 24篇 |
2001年 | 18篇 |
2000年 | 29篇 |
1999年 | 7篇 |
1998年 | 6篇 |
1997年 | 8篇 |
1996年 | 4篇 |
1995年 | 4篇 |
1994年 | 6篇 |
1993年 | 1篇 |
1989年 | 1篇 |
1988年 | 2篇 |
排序方式: 共有1328条查询结果,搜索用时 15 毫秒
101.
Comparative study of kinetic modeling for the oxidative coupling of methane by genetic and marquardt algorithms 总被引:1,自引:0,他引:1
下载免费PDF全文
![点击此处可从《天然气化学杂志》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Overall kinetic studies on the oxidative coupling of methane, OCM, have been conducted in a tubular fixed bed reactor, using perovskite titanate as the reaction catalyst. The appropriate operating conditions were found to be: temperature 750-775 ℃, total feed flow rate of 160 ml/min, CH4/O2 ratio of 2 and GHSV of 100 min-1. Under these conditions, C2 yield of 28% was achieved. Correlations of the kinetic data have been performed with lumped rate equations for C2 and COx formation as functions of temperature, O2 and CH4 partial pressures. Six models have been selected among the common lumped kinetic models. The selected models have been regressed with the experimental data which were obtained from the Catatest system by genetic algorithm in order to obtain optimized parameters. The kinetic coefficients in the overall reactions were optimized by different numerical optimization methods such as: the Levenberg-Marquardt and genetic algorithms and the results were compared with one another. It has been found that the Santamaria model is in good agreement with the experimental data. The Arrhenius parameters of this model have been obtained by linear regression. It should be noted that the Marquardt algorithm is sensitive to the first guesses and there is possibility to trap in the relative minimum. 相似文献
102.
LaSrMnNbO6 has been synthesized by high temperature solid state reaction under 1% H2/Ar dynamic flow. The structure is determined by Rietveld refinement of the powder X-ray diffraction data. It crystallizes in the monoclinic space group P21/n with the unit cell parameters: a=5.69187(12), b=5.74732(10), c=8.07018(15) Å and β=90.0504(29)°, which were also confirmed by electron diffraction. The Mn2+ and Nb5+ ions, whose valence states are confirmed by X-ray absorption near-edge spectroscopy, are almost completely ordered over the B-site (<1% inversion) of the perovskite structure due to the large differences of both cationic size (0.19 Å) and charge. The octahedral framework displays significant tilting distortion according to Glazer’s tilt system a−b−c+. Upon heating, LaSrMnNbO6 decomposes at 690 °C under O2 flow or at 775 °C in air. The magnetic susceptibility data indicate the presence of long-range antiferromagnetic ordering at TN=8 K; the experimentally observed effective paramagnetic moment, μeff=5.76 μB for high spin Mn2+ (3d5, S=5/2) is in good agreement with the calculated value (μcalcd=5.92 μB). 相似文献
103.
S. Vasala Y.H. Huang H. Yamauchi M. Karppinen 《Journal of solid state chemistry》2010,183(5):1007-1012
We have investigated a series of double-perovskite oxides Sr2MMoO6−δ (M=Mg, Mn, Fe, Co, Ni, Zn) for redox stability, oxygen content and crystal structure. Phases with M=Co, Ni and Zn were found to be oxygen-stoichiometric and stable under oxidizing conditions, whereas those with M=Mn and Fe were oxygen-deficient and stable under reducing conditions. The M=Mg phase is stable both under reducing and oxidizing conditions, showing variable oxygen contents within 0.00≤δ≤0.04 depending on the annealing conditions. Structural data indicate somewhat depressed values for the degree of M/Mo cation order and also evidence of electron transfer from MII to MoVI for M=Mn, Fe and Co. 相似文献
104.
Heqing Jiang Dr. Fangyi Liang Oliver Czuprat Konstantin Efimov Armin Feldhoff Dr. Steffen Schirrmeister Dr. Thomas Schiestel Dr. Haihui Wang Prof. Jürgen Caro Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(26):7898-7903
A porous perovskite BaCoxFeyZr0.9?x?yPd0.1O3?δ (BCFZ‐Pd) coating was deposited onto the outer surface of a BaCoxFeyZr1?x?yO3?δ (BCFZ) perovskite hollow‐fiber membrane. The surface morphology of the modified BCFZ fiber was characterized by scanning electron microscopy (SEM), indicating the formation of a BCFZ‐Pd porous layer on the outer surface of a dense BCFZ hollow‐fiber membrane. The oxygen permeation flux of the BCFZ membrane with a BCFZ‐Pd porous layer increased 3.5 times more than that of the blank BCFZ membrane when feeding reactive CH4 onto the permeation side of the membrane. The blank BCFZ membrane and surface‐modified BCFZ membrane were used as reactors to shift the equilibrium of thermal water dissociation for hydrogen production because they allow the selective removal of the produced oxygen from the water dissociation system. It was found that the hydrogen production rate increased from 0.7 to 2.1 mL H2 min?1 cm?2 at 950 °C after depositing a BCFZ‐Pd porous layer onto the BCFZ membrane. 相似文献
105.
Effect of Copper Substitution and Preparation Methods on the LaMnO3 Structure and Catalysis of Methane Combustion and CO Oxidation 总被引:1,自引:0,他引:1
LaMn1-xCuxO3刡冊 perovskite oxides (x = 0, 0.2, 0.4, 0.6, 0.8, 1) were prepared by two different methods, the Pechini and sol-gel methods. The catalysts were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), X-ray fluorescence spectroscopy, N2 adsorption, and temperature-programmed reduction. Their catalytic activity in the oxidation of methane and CO was evaluated. EDS and SEM results showed that the Pechini samples had more homogeneity and smaller particles (higher specific surface area). The catalytic activity for methane combustion was highest for x = 0.2. In CO oxidation, the oxides with x = 0.2 and x = 0.4 were the most active. The Pechini samples had higher activity and stability than the sol-gel samples. 相似文献
106.
A single phase rare earth double perovskite oxide Ba2CeNbO6 (BCN) is synthesized by solid-state reaction technique for the first time. The X-ray diffraction pattern of the sample at room temperature shows monoclinic structure, with the lattice parameters, a=5.9763 Å, b=5.975 Å and c=8.48 Å and β=90.04°. Impedance spectroscopy is used to study the ac electrical behavior of this material as a function of frequency (102-106 Hz) at various temperatures (30-450 °C). A relaxation is observed in the entire temperature range. Conduction mechanism is investigated by fitting the complex impedance data to Cole-Cole equation. Complex impedance plane plots show only one semicircular arc, indicating only the grain contribution of dielectric relaxation. The scaling behavior of imaginary part of electric modulus (M″) and imaginary part of electrical impedance (Z″) suggests that the relaxation describes the same mechanism at various temperatures. The frequency dependence of conductivity is interpreted in terms of the jump relaxation model and is fitted to Jonscher's power law. The values of dc conductivities extracted from the Jonscher power law varies from 2.79×10−7 to 3.5×10−5 Sm−1 with the increase in temperature from 100 to 450 °C. The activation energies (0.37 eV) extracted from M″(ω) and Z″(ω) peaks are found to follow the Arrhenius law. 相似文献
107.
108.
109.
110.
L. Patron O. Carp I. Mandru G. Grasa 《Journal of Thermal Analysis and Calorimetry》1999,56(2):597-602
New Nd-Co based polynuclear coordination compounds containing as ligand polyhydrocarboxylic acid as tartaric, malic and gluconic
acids were prepared, namely: [NdCo(tart)3]·4H2O, (NH4)[NdCo0.5Cu0.5(tart)3]·4H2O, (NH4)[NdCo(malic)3]·4H2O, (NH4)[NdCo0.5Cu0.5(malic)3]·4H2O, [NdCo(gluc)4]·4H2O and [Nd2CoCu(gluc)7]·5H2O. A comparison between the thermal behaviour of the studied polynuclear coordination compounds concerning thermal stability
and thermal decomposition stoichiometry was inferred. Oxalic and malonic intermediates were identified at about 300°C in the
thermal decomposition of tartaric and malic compounds. In all the decomposition processes at about 400°C the presence of oxocarbonate
is shown. The residual products are mixed oxides of perovskite type.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献