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991.
A new differential pulse polarographic method for the determination of W(VI) using a catalytic adsorption wave is described. W(VI) is first chelated by 7-iodo-8-hydroxyquinoline-5-sulfonic acid at pH 0.5. The complex ion formed is strongly adsorbed on the surface of a dropping mercury electrode. At a potential of –0.95 V versus the Ag/AgCl (3M KCl) reference electrode the adsorbed complex is reduced by the polarographic current and oxidized very fast by hydrated hydrogen ions providing the oxidized form of the complex ion for repeated redox cycles. As the redox process taking place in the electric double layer, the diffusion of the complex does not limit the polarographic current. Therefore, high currents occur, and consequently, a very high sensitivity is obtained. The practical detection limit (PDL) is 3.7 ng W/kg solution corresponding to 2 × 10–11
M. The standard deviation of single values is 1.2 ng/kg at the concentration of 91 ng/kg lying in the middle of the linear part of the calibration curve. Because Mo (VI) gives a very similar catalytic adsorption wave, serious mutual interferences occur in the analysis of mixtures of both species. An effective separation of Mo(VI) was worked out. Using 1% (w/v) solution of trioctylphosphinoxide in kerosene, Mo(VI) can almost completely be extracted from 1.8M HCl with a threefold extraction resulting in a separation factor of 40000. 相似文献
992.
A new niobate compound with the chemical composition of Ba5LiTiNb9O30 was synthesized by doping Li^ into the system BaO-TiO2-Nb2O5 in conventional solid state reaction method. The crystalline structure was determined by X-ray diffraction analysis (XRD). The results showed that crystal structure of Ba5LiTiNb9O30 belongs to tetragonal tungsten bronze structure with space group P4bm and its unit cell parameters: a=b=1.2512(2) nm, c=0.4008(5)nm. The microstructure of reaction products was observed by scanning electron microscopy (SEM). 相似文献
993.
(NH3CH2CH2NH2)3[Mo(Ⅴ)O2(O2C6H4)2] (1), (NH3CH2CH2NH2)2.5[Mo(Ⅴ)o.sW(Ⅵ)o.502(O2C6H4)2] (2) and(NH3CH2CH2NH2)2[VC(Ⅵ)O2(O2C6H4)2] (3) were synthesized, structurally characterized by X-ray diffraction analysis, and studied on their interactions with ATP, their DNA cleavage activities and antitumor properties. The redox state of molybdenum was not changed on going from crystal to aqueous solutions in complexes 1 and 2, while tungsten underwent reduction from W(VI) to W(V) in complexes 2 and 3. ATP promoted the oxidation of both molybdenum and tungsten from M(Ⅴ) to M(Ⅵ) and the hydrolysis of catecholate ligands in solution consisting of ATP and the complexes. Complex 1 possesses fairly good activity to DNA cleavage and against tumor S180 in mice, and is more effective than the control drug cyclophosphamide under the identical conditions. However, complexes 2 and 3 exhibited marginal effectiveness. The effectiveness of anti-tumor of the complexes was related positively to their DNA cleavage activities and their hydrolysis of catecholate ligands. 相似文献
994.
Yagi M Sone K Yamada M Umemiya S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(2):767-775
A tungsten trioxide (WO(3))/tris(2,2'-bipyridine)ruthenium(II) ([Ru(bpy)(3)](2+); bpy=2,2'-bipyridine)/poly(sodium 4-styrenesulfonate) (PSS) hybrid film was prepared by electrodeposition from a colloidal triad solution containing peroxotungstic acid (PTA), [Ru(bpy)(3)](2+), and PSS. A binary solution of [Ru(bpy)(3)](2+) and PTA (30 vol % ethanol in water) gradually gave an orange precipitate, possibly caused by the electrostatic interaction between the cationic [Ru(bpy)(3)](2+) and the anionic PTA. The addition of PSS to the binary PTA/[Ru(bpy)(3)](2+) solution remarkably suppressed this precipitation and caused a stable, colloidal triad solution to form. The spectrophotometric measurements and lifetime analyses of the photoluminescence from the excited [Ru(bpy)(3)](2+) ion in the colloidal triad solution suggested that the [Ru(bpy)(3)](2+) ion is partially shielded from electrostatic interaction with anionic PTA by the anionic PSS polymer chain. The formation of the colloidal triad made the ternary [Ru(bpy)(3)](2+)/PTA/PSS solution much more redox active. Consequently, the rate of electrodeposition of WO(3) from PTA increased appreciably by the formation of the colloidal triad, and fast electrodeposition is required for the unique preparation of this hybrid film. The absorption spectrum of the [Ru(bpy)(3)](2+) ion in the film was close to its spectrum in water, but the photoexcited state of the [Ru(bpy)(3)](2+) ion was found to be quenched completely by the presence of WO(3) in the hybrid film. The cyclic voltammogram (CV) of the hybrid film suggested that the [Ru(bpy)(3)](2+) ion performs as it is adsorbed onto WO(3) during the electrochemical oxidation. An ohmic contact between the [Ru(bpy)(3)](2+) ion and the WO(3) surface could allow the electrochemical reaction of adsorbed [Ru(bpy)(3)](2+). The composition of the hybrid film, analyzed by electron probe microanalysis (EPMA), suggested that the positive charge of the [Ru(bpy)(3)](2+) ion could be neutralized by partially reduced WO(3)(-) ions, in addition to Cl(-) and PSS units, based on the charge balance in the film. The electrostatic interaction between the WO(3)(-) ion and the [Ru(bpy)(3)](2+) ion might be responsible for forming the electron transfer channel that causes the complete quenching of the photoexcited [Ru(bpy)(3)](2+) ion, as well as the formation of the ohmic contact between the [Ru(bpy)(3)](2+) ion and WO(3). A multicolor electrochromic performance of the WO(3)/[Ru(bpy)(3)](2+)/PSS hybrid film was observed, in which transmittances at 459 and 800 nm could be changed, either individually or at once, by the selection of a potential switch. Fast responses, of within a few seconds, to these potential switches were exhibited by the electrochromic hybrid film. 相似文献
995.
《Surface and interface analysis : SIA》2005,37(7):615-620
This article investigates the nitridation effect of InP(100) semiconductor surfaces performed using a glow discharge cell. Auger electron spectroscopy and XPS were used to understand the different steps of this process. An important point is the initial quantity of metallic indium on the InP(100) surfaces. Indeed the indium droplets, created in well‐known quantity, play the role of precursor. At a relatively low temperature of 523 K the system undergoes surface restructuring, which includes removal of the In droplets and the formation of two InN monolayers. Phosphorus–nitrogen bonds have been detected by the analysis of P LMM Auger peaks, and In? N bonds by analysis of the In 4d XPS peak. However, the presence or not of metallic indium inside this InN overlayer is crucial for passivation of the substrate. Ex situ photoluminescence measurements correlated to the electron spectroscopies results have shown the good passivation effect of the InP(100) surfaces by InN overlayers for 40 min of nitridation. Copyright © 2005 John Wiley & Sons, Ltd. 相似文献
996.
Khalil J. Asali Tino Ladogana Simon G. Bott Gerard R. Dobson 《Journal of chemical crystallography》2003,33(9):701-704
The title compound crystallizes in the centrosymmetric triclinic unit cell, a = 6.6662(8) Å, b = 8.8584(6) Å, c = 13.574(2) Å, = 71.468(7)°, = 82.182(9)°, = 75.270(7)°, Z = 1. Refinement converged at R = 0.0396 for 1383 observed reflections. The molecule consists of two W(CO)5 fragments bridged centrosymmetrically by the 2,2,9,9-tetramethyl-3,7-dithiadecane ligand. 相似文献
997.
采用软模板法制备了氮化钨-钨/掺氮有序介孔碳复合材料(WN-W/NOMC),作为一种高比表面积且价格低廉的阴极氧还原反应催化剂。通过适量添加尿素来改变复合材料中的氮含量,在掺氮量为7%(w/w)时,实验发现材料能够保持完整有序介孔结构,测试其比表面积高达835 m~2·g~(-1),透射电子显微镜(TEM)测试结果显示其催化颗粒均匀地分散在氮掺杂有序介孔碳载体上。在O_2饱和的0.1 mol·L~(-1 )KOH溶液中测试了材料的氧还原催化性能(ORR),显示其起始电位为0.87 V(vs RHE),极限电流密度为4.49 mA·cm~(-2),氧还原反应的转移电子数为3.4,接近于20%(w/w)商业Pt/C的3.8,说明该材料表现出近似4电子的氧还原反应途径。研究结果表明,WN-W/NOMC的催化性能虽然稍弱于商业铂碳(0.99 V,5.1 mA·cm~(-2)),但其具有远超铂碳的循环稳定性和耐甲醇毒化能力。 相似文献
998.
Satoshi Kamiguchi Sayoko Nagashima Kin-ichi Komori Mitsuo Kodomari Teiji Chihara 《Journal of Cluster Science》2007,18(2):414-430
When the molecular tungsten halide cluster (H3O)2[(W6Cl8)Cl6]·6H2O, with an octahedral metal framework, is heated to 50 and 150 °C in flowing helium gas, it changes into (H3O)2[(W6Cl8)Cl6] and [(W6Cl8)Cl4(H2O)2], respectively. Activation at 250 °C yields a poorly crystallized solid state cluster, [W6Cl8]Cl2Cl4/2, which exhibits catalytic activity for the dehydration of ethanol to yield ethylene and a small amount of ethyl ether and
acetal. The activity is attributed to the Br?nsted acidity of the hydroxo ligand that is produced by elimination of hydrogen
chloride from the chloro and aqua ligands. The catalytic activity increases with increasing temperature, and reaches a maximum
at 300 °C. The catalytic activity then disappears above 350 °C, at which temperature the crystallinity of the cluster improves
and the active sites are included in the crystal. In the case of primary alcohols, the reactivity decreases with increasing
length of the carbon chain, and secondary alcohols are more reactive than the corresponding primary alcohols. Halide clusters
of niobium, molybdenum, and tantalum having the same metal framework are also active catalysts for these reactions. 相似文献
999.
In this work, the tunneling breakdown of n-InP electrode using large signal current density step has been investigated. The influence of current density on the tunneling breakdown is not obvious, but the light intensities affect the breakdown severely. Some parameters are calculated during breakown and explained. 相似文献
1000.