全文获取类型
收费全文 | 219篇 |
免费 | 5篇 |
国内免费 | 4篇 |
专业分类
化学 | 30篇 |
晶体学 | 1篇 |
力学 | 1篇 |
物理学 | 196篇 |
出版年
2023年 | 7篇 |
2022年 | 14篇 |
2021年 | 18篇 |
2020年 | 29篇 |
2018年 | 13篇 |
2017年 | 22篇 |
2016年 | 26篇 |
2015年 | 8篇 |
2014年 | 34篇 |
2013年 | 5篇 |
2012年 | 17篇 |
2011年 | 4篇 |
2010年 | 6篇 |
2009年 | 4篇 |
2008年 | 3篇 |
2007年 | 3篇 |
2006年 | 2篇 |
2005年 | 1篇 |
2004年 | 1篇 |
2003年 | 1篇 |
2002年 | 2篇 |
2001年 | 2篇 |
2000年 | 2篇 |
1999年 | 1篇 |
1997年 | 1篇 |
1996年 | 2篇 |
排序方式: 共有228条查询结果,搜索用时 15 毫秒
61.
Sonolysis of chlorobenzene in Fenton-type aqueous systems 总被引:4,自引:0,他引:4
The influence of ultrasounds (200 kHz frequency) on the decomposition of chlorobenzene (CB) in a water solution (around 100 ppm concentration) containing iron or palladium sulfates was investigated. The intermediates of the sonolysis were identified, thus allowing a deeper insight into the degradation mechanism. It was established that CB degradation starts by pyrolysis inside the cavitation bubbles. The initial sonolysis product is benzene, formed in a reaction occurring outside the cavitation from phenyl radicals and the hydrogen atoms sonolytically generated from the water. Polyphenols as products of the CB sonochemical degradation are reported for the first time. The palladium salt was found to be a useful and sensitive indicator for differentiating the sites and mechanisms of the product formation. An alternative mechanism for the CB sonolysis is advanced, explaining the formation of phenols, polyphenols, chlorophenols and benzene. 相似文献
62.
Propelled by enormous increase in demand for fuel sources, Canadian oil sands are becoming increasingly important as a fuel source due to their abundance and upgrading capability. However, extraction of bitumen, a high acid crude (HAC) oil, requires 2–3 units of water per unit of oil resulting in naphthenic acid (NA)-rich oil sands process affected water (OSPW) collected in effluent ponds. This study illustrates the role of sonochemistry in the accelerated degradation through H-abstraction and subsequent decarboxylation of aromatic and alicyclic naphthenic acid model compounds. Benzoic acid and 3-methylcyclohexane carboxylic acid were selected as model NA compounds to investigate the mechanism of hydroxyl radical (OH•) initiated carboxylic acid degradation in 378 KHz sonochemical reactor. Established FTIR methods with low resolution LCMS spectroscopy confirmation were applied to determine the extent of carboxylic acid degradation and identify the formation of products. FTIR monitoring showed a non-linear degradation of carboxylic acids with formation of many intermediates highlighting the shift from cyclic carboxylic acids to cyclic alcohols during BA degradation. Subsequent decrease in carboxylic acid groups signifies scission of cyclic structures before complete mineralization. This is confirmed with the LCMS identification of products such as: 3-hydroxybenzoic acid and phenol. This study postulated new breakdown pathways for degradation of benzoic acid with complete mineralization at a sonochemical reaction time (SRT) of 4 h. A radical quenching process was also inferred through the formation of conglomerates during sonochemical degradation of BA. Extension of the study to 3-methylcyclohexane carboxylic acid (3mCHA) shows similar non-linearity with an increase in carboxylic acid groups indicating H-abstraction followed by ring-opened compounds. However, due to the complex nature of 3mCHA’s ring-opened compounds, complete mineralization is not achieved. The putative role of sonochemistry is a promising and sustainable degradation method for mitigating NAs in OSPW, but sonication periods need to be considered carefully to ensure adequate mineralization of their constituents and combinatorial methods with other advanced oxidation methods may be needed to enhance industrial application.In Part II, an in silico screening approach using first principles is reported to identify the breakdown of the organic compounds and determine molecular rates of reaction to confirm the mechanistic origins of the compounds formed. 相似文献
63.
A series of arylhydrazines was synthesized from the reaction mixture of Mg powder, 1,2‐dibromoethane, aryl bromide and DEAD (diethyl azodicarboxylate) in THF under ultrasound. This sonochemical Barbier reaction provides an efficient and inexpensive preparation method for synthesis of arylhydrazines. 相似文献
64.
两种不同类型的声场与声化学产额的关系 总被引:7,自引:0,他引:7
采用声源频率为1.8 MHz的连续声波在声强0~5 W•cm-2间,研究了连续混响声场中声化学产领(以溶液的电导率改变、溶液pH值改变和KI溶液的I2析出量以及空化水中的水合负电子()表征)与声强和超声辐照时间之间的关系.理论推论与实验结果均表明,连续声场中声化学产额与声强、超声辐照时间之间呈线性关系.并证明了声场中声化学反应动力学方程具有简单线性关系,与Henglein等人对脉冲声场中声化学产额与声场参数之间呈非线性关系的研究结果比较,证明对实际工业化运行的声化学反应器,采用连续声波更利于目标反应生成物的控制。 相似文献
65.
A new Co(II) mixed-ligand coordination supramolecular polymer with composition [Co2(ppda)(4-bpdh)2(NO3)2]n (1) (where, ppda = p-phenylenediacrylic acid, 4-bpdh = 2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene) was synthesized using solvothermal, mechanochemical and sonochemical methods. Compound 1 and the new nanostructure have been characterized by single-crystal X-ray, infrared spectroscopy (IR), powder X-ray diffraction (PXRD) analysis and scanning electron microscopy (SEM). The thermal stability of compound 1 was also studied by thermal gravimetric analysis (TGA). The surface area of these compounds was determined by BET. The single-crystal X-ray data shows a new interesting two-dimensional coordination polymer (CP). In addition, the effect of various sonication concentrations of initial reagents, power of ultrasound irradiation and also the time on the size and morphology of nano-structured coordination polymer 1 were evaluated. Moreover, it has been demonstrated that the nanostructure of the CP1 can be used as a catalyst in Knoevenagel condensation reaction. 相似文献
66.
Ultrasound was used to synthesize nano-structures of [Ni(bpzB)2]2(1), a new two-nuclear discrete-coordination compound of divalent nickel with bis-pyrazolyl borate(bpzB). The nanostructure was characterized by scanning electron microscopy, X-ray powder diffraction, infrared, and elemental analysis. The single-crystal X-ray data show that the coordination number of Ni(II) ions is four (Ni1N4 and Ni2N4) with square planar geometry. The supramolecular features in these complexes are guided and controlled by weak directional intermolecular interactions. The discrete molecules interact with each other through labile interactions, creating a 3D supramolecular framework. 相似文献
67.
Numerical simulation of cavitation bubble dynamics induced by ultrasound waves in a high frequency reactor 总被引:2,自引:0,他引:2
The use of high frequency ultrasound in chemical systems is of major interest to optimize chemical procedures. Characterization of an open air 477 kHz ultrasound reactor shows that, because of the collapse of transient cavitation bubbles and pulsation of stable cavitation bubbles, chemical reactions are enhanced. Numerical modelling is undertaken to determine the spatio-temporal evolution of cavitation bubbles. The calculus of the emergence of cavitation bubbles due to the acoustic driving (by taking into account interactions between the sound field and bubbles' distribution) gives a cartography of bubbles' emergence within the reactor. Computation of their motion induced by the pressure gradients occurring in the reactor show that they migrate to the pressure nodes. Computed bubbles levitation sites gives a cartography of the chemical activity of ultrasound. Modelling of stable cavitation bubbles' motion induced by the motion of the liquid gives some insight on degassing phenomena. 相似文献
68.
Mahito Atobe Mayuko Okamoto Toshio Fuchigami Jong-Eun Park 《Ultrasonics sonochemistry》2010,17(1):26-29
Polypyrrole-encapsulated platinum nanoparticles (PPy/Pt-NPs) prepared by an easy single-step sonochemical synthesis were used as catalysts for the liquid phase hydrogenation of substituted alkenes in methanol or methanol/water mixtures. Polypyrrole (PPy) coatings on the nanoparticles were able to act as nanoscopic filters for substrates molecules, and consequently substrate selectivity could be controlled in the catalytic processes. 相似文献
69.
We are reporting on the synthesis of Mn3O4 nanoparticles and CTAB-Mn3O4 nanocomposites via a sonochemical route using MnCl2, ethanol, NaOH and CTAB. The crystalline phase was identified as Mn3O4. The crystallite size of the CTAB-Mn3O4 nanocomposite was identified as 13 ± 5 nm from X-ray line profile fitting and the particle size from TEM was 107.5 ± 1.4 nm. The interaction between CTAB and the Mn3O4 nanoparticles was investigated by FTIR and 1H NMR spectroscopies. Two different magnetic phase transitions were observed for both samples below the Curie temperature (43 °C) by using a low temperature Electron Paramagnetic Resonance (EPR) technique. Also we determined the effect of the capping with CTAB on the reduction in absorbed power. 相似文献
70.
R. Kalai Selvan A. Gedanken P. Anilkumar G. Manikandan C. Karunakaran 《Journal of Cluster Science》2009,20(2):291-305
We report herein on an efficient sonochemical method for the synthesis of rare earth orthovanadate nanorods/nanoparticles/nanospindles,
(general formula RVO4; R = La, Ce, Nd, Sm, Eu and Gd). TGA, XRD, FTIR, Raman, UV–Vis, and TEM studies are employed for their characterization and
for understanding their morphologies. In order to vary the textural properties of the rare earth vanadates, two surfactants,
polyethylene glycol (PEG) and amphiphilic triblock copolymer Pluronic P123, are chosen in the preparation. While the sonochemical
synthesis in the presence of PEG results in the formation of nearly spherical nanoparticles of LaVO4, CeVO4, SmVO4 and EuVO4, the same technique yields nanorods and nanospindles of NdVO4 and GdVO4, respectively. When P123 is used as the surfactant, the morphologies of RVO4 are strikingly different, and in most cases nanorods and nanospindles are formed. The photocatalytic activities of the rare
earth orthovanadate have been evaluated by studying the degradation of methylene blue, and CeVO4 seems to be the best catalyst in the heterogeneous photolysis. The electrocatalytic activity of the vanadates has been examined
by studying the hydrogen evolution reaction using a linear sweep voltammogram technique in 1 M of a H2SO4 solution. GdVO4 seems to be the best electrocatalyst.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献