全文获取类型
收费全文 | 2685篇 |
免费 | 324篇 |
国内免费 | 687篇 |
专业分类
化学 | 2361篇 |
晶体学 | 39篇 |
力学 | 66篇 |
综合类 | 18篇 |
数学 | 30篇 |
物理学 | 1182篇 |
出版年
2024年 | 15篇 |
2023年 | 197篇 |
2022年 | 123篇 |
2021年 | 165篇 |
2020年 | 148篇 |
2019年 | 74篇 |
2018年 | 110篇 |
2017年 | 130篇 |
2016年 | 117篇 |
2015年 | 138篇 |
2014年 | 153篇 |
2013年 | 172篇 |
2012年 | 139篇 |
2011年 | 214篇 |
2010年 | 132篇 |
2009年 | 183篇 |
2008年 | 159篇 |
2007年 | 187篇 |
2006年 | 185篇 |
2005年 | 106篇 |
2004年 | 118篇 |
2003年 | 109篇 |
2002年 | 69篇 |
2001年 | 63篇 |
2000年 | 55篇 |
1999年 | 48篇 |
1998年 | 55篇 |
1997年 | 59篇 |
1996年 | 48篇 |
1995年 | 31篇 |
1994年 | 22篇 |
1993年 | 31篇 |
1992年 | 24篇 |
1991年 | 16篇 |
1990年 | 18篇 |
1989年 | 18篇 |
1988年 | 12篇 |
1987年 | 7篇 |
1986年 | 7篇 |
1985年 | 9篇 |
1984年 | 3篇 |
1983年 | 3篇 |
1982年 | 7篇 |
1980年 | 3篇 |
1979年 | 5篇 |
1976年 | 2篇 |
1974年 | 2篇 |
1972年 | 1篇 |
1971年 | 1篇 |
1967年 | 1篇 |
排序方式: 共有3696条查询结果,搜索用时 203 毫秒
101.
Delano P. Chong 《中国化学会会志》1992,39(5):457-459
The vertical ionization potentials of OF2, HNF2, and CH2F2 were computed by the deMon density functional program. The results are compared with earlier calculations and with experiment. The average absolute deviation of the 21 computed ionization potentials of the outer valence electrons from experiment is 0.44 eV, which compares well with 0.37 eV for frozen-orbital configuration-interaction calculations. Although this performance is not as good as perturbation corrections to Koopmans' theorem, the computation requirements are much less demanding. 相似文献
102.
Thermal decomposition of some hydrocarbon and chlorinated hydrocarbon compounds in metal capillary tubes used in an inlet system for high speed gas chromatography has been investigated. The metal tube is cooled to about ?75°C by a flow of cold nitrogen gas in order to focus a vapor sample cryogenically. A capacitive discharge power supply is then used to heat the metal tube resistively in order to revaporize the sample and introduce it to the separation column as a plug 5-10 ms wide. The effects of tube temperature, tube material, sample vapor residence time, and type of carrier gas on thermal cracking are described. Use of a copper-nickel alloy tube resulted in less cracking than either pure platinum or pure nickel. Cracking is more significant with hydrogen as carrier gas than with helium. Cracking also increases with increasing sample residence time in the hot tube. Quantitative sample injection with minimum decomposition can be obtained for a variety of aliphatic and aromatic hydrocarbons and chlorinated hydrocarbon compounds. 相似文献
103.
A membrane having an amine moiety was prepared by plasma-grafting 2-(N,N-dimethyl)aminoethyl methacrylate (DAMA) onto a microporous polyethylene substrate. Permselectivity of the membrane for CO2 over N2 was achieved in both dry and water swollen conditions. When the CO2 partial pressure in the feed gas was 0.047 atm, the selectivity of CO2 over N2 reached 130 for the highly swollen water containing membrane. This value was found to agree with that obtained with a mobile carrier membrane (supported liquid membrane) using DAMA as the carrier. The effects of several experimental conditions such as degree of grafting, feed partial pressure and temperature on the membrane performance were studied. It was suggested that the membrane acted as a fixed carrier membrane for CO2 facilitated transport in under the dry condition and acted as a fixed reaction site membrane in the water swollen condition. The carrier transport mechanism is discussed for dry and aqueous membranes. 相似文献
104.
Wei-Cho Huang Cheng S. Gong George T. Tsao 《Applied biochemistry and biotechnology》2003,106(1-3):471-480
Pressure pulsation (PP) was investigated for its effects on oxygen transfer rate (OTR) measured by sulfite oxidation. By manipulating
airflow rate, 0.41–1.2 vvm, and a control valve in a 4-L bioreactor, the frequency of PP was varied at different gas pressures3–15
psig. A mathematical model of OTR was built and compared to experimental data. OTR was also examined at constant gas pressure,
4.5–15.0 psig. The results indicate a good agreement between measurement and model prediction. OTR above 9 psig during PP
showed significant enhancement at 25°C. This proves that PP not only affects the elevation of DO level, but also increases
the interfacial area and mass transfer coefficient. 相似文献
105.
《Electroanalysis》2004,16(17):1444-1450
The multi‐walled carbon nanotubes (MWNTs) modified glassy carbon electrode exhibited electrocatalytic activity to the reduction of oxygen in 0.1 M HAc‐NaAc (pH 3.8) buffer solution. Further modification with cobalt porphyrin film on the MWNTs by adsorption, the resulted modified electrode showed more efficient catalytic activity to O2 reduction. The reduction peak potential of O2 is shifted much more positively to 0.12 V (vs. Ag/AgCl), and the peak current is increased greatly. Cyclic voltammetry (CV), transmission electron microscopy (TEM), X‐ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM), were used to characterize the material and the modified film on electrode surface. Electrochemical experiments gave the total number of electron transfer for oxygen reduction as about 3, which indicated a co‐exist process of 2 electrons and 4 electrons for reduction of oxygen at this modified electrode. Meanwhile, the catalytic activities of the multilayer film (MWNTs/CoTMPyP)n prepared by layer‐by‐layer method were investigated, and the results showed that the peak current of O2 reduction increased and the peak potential shifted to a positive direction with the increase of layer numbers. 相似文献
106.
107.
Elena V. Frolova M. Ivanovskaya V. Sadykov G. Alikina A. Lukashevich S. Neophytides 《Progress in Solid State Chemistry》2005,33(2-4):317-325
Structural peculiarities of Ce–Zr–La–O and Ce–Zr–La–O/Ru samples in mean of catalytic properties are compared. The samples (Ce:Zr = 1:1, La = 10÷30 mol.%, Ru = 1.5 wt.%) were obtained by sol–gel method (X-samples) and co-precipitation (P-samples). It is shown that Ce0.45Zr0.45La0.1O2−δ/Ru X-samples are characterized by high thermal stability and the highest catalytic activity in partial methane oxidation reaction. According to XRD, BET, FTIR, EPR and XPS data it is concluded that the difference in the samples catalytic activity is caused by various disposition of Ru-containing phase on the support surface. The distinction in the dimension of Ru-containing particles (3D or 2D) is conditioned by structural peculiarities of Ce0.45Zr0.45La0.1O2−δ and Ce0.35Zr0.35La0.3O2−δ P- and X-samples. 相似文献
108.
Stefan?DiethelmEmail author Joseph?Sfeir Frank?Clemens Jan?Van herle Daniel?Favrat 《Journal of Solid State Electrochemistry》2004,8(9):611-617
Dense planar and tubular oxygen separation membranes of La0.6Ca0.4Fe0.75Co0.25O3– were investigated as reactors for the partial oxidation (POX) of methane to syngas. Their permeation properties were measured in an air/argon
pO2 gradient as a function of temperature. At 900 °C, the oxygen flux through a 1.26-mm-thick membrane was 0.075 mol/cm2·s and through a 0.25-mm-thick tube, 0.24 mol/cm2·s.For the POX measurements, a catalyst was added to the membrane and methane was introduced on the argon side. This resulted in a gradual increase of the oxygen flux with increasing concentration of methane, reaching 2 mol/cm2·s at 900 °C with pure methane. For the planar reactor, the CO selectivity reached 99% and the CH4 conversion 75% at 918 °C with pure methane. For the tubular reactor, the CO selectivity and CH4 conversion were 83 and 99%, respectively, under the same conditions. After 1,400 h of operation in a tubular POX reactor, the membrane was examined revealing phase demixing and local decomposition.Presented at the OSSEP Workshop Ionic and Mixed Conductors: Methods and Processes, Aveiro, Portugal, 10–12 April 2003 相似文献
109.
The silver iodate(VII), Ag5IO6, was obtained by reacting a stoichiometric mixture of Ag2O and KIO3, at elevated oxygen pressure, adding a small portion of distilled water. The synthesis was done at 673 K and 270 MPa of oxygen pressure. The crystal structure was solved by direct methods based on single crystal diffraction data ( , Z = 6, a = 5.9366(1), c = 32.1471(6) Å, 323 independent reflections, R1 = 2.31 %). According to conductivity measurements, Ag5IO6 is semiconducting with a specific resistance of 0.08 Ωcm at 300 K. The activation energy was determined as 7.4(1) meV in the temperature range of 220 – 300 K, and 4.3(1) meV in the temperature range of 90 – 180 K. The optical band gap for Ag5IO6 is 1.4 eV. Ag5IO6 is diamagnetic with a magnetic susceptibility of ?4.4×10?4 emu/mol. 相似文献
110.
纳米碳管电极上氧的电催化还原 总被引:5,自引:0,他引:5
以聚四氟乙烯为粘结剂制成了多壁纳米碳管(MWNT)电极.采用恒电位阶跃法和循环伏安法研究了MWNT电极在碱性溶液中的电化学行为,并对碱性溶液中溶解氧在该电极上的电化学还原行为进行了研究.实验结果表明: MWNT电极具有比石墨电极更高的孔隙率和电化学表面积;MWNT电极上O2还原成的反应为准可逆过程;在5~50 mV•s-1的扫描速率范围内,阴极峰电流与扫描速度成线性关系,表明MWNT电极上O2还原成的反应受吸附控制;对碱性溶液中的氧还原反应, MWNT比石墨具有更高的催化活性. 相似文献