Kinetics of oxidation of benzyl alcohols with molecular oxygen catalyzed by N-hydroxyphthalimide: Role of hydroperoxyl radicals

A kinetic study of the initiated oxidation of benzyl alcohol and cumene by molecular oxygen was performed. The oxidation rate was more enhanced with N-hydroxyphthalimide (NHPI) in the case of cumene than that of benzyl alcohol. HOOH inhibits cumene oxidation and does not affect the rate of oxidation of benzyl alcohol. It was shown that termination chain reactions of phthalimid-N-oxyl radicals (PINO^•) does not occur with RОО^• and proceeds with HOO^•. A kinetic scheme of the process and an equation describing the kinetics of oxidation of benzyl alcohol in the presence of NHPI are proposed. Using the PM7 method, the thermodynamic characteristics of elementary steps of oxidation explaining the obtained results were calculated.     

Dynamic headspace liquid-phase microextraction of alcohols

A method was developed using dynamic headspace liquid-phase microextraction and gas chromatography-mass spectrometry for extraction and determination of 9 alcohols from water samples. Four different solvents, hexyl acetate, n-octanol, o-xylene and n-decane were studied as extractants. The analytes were extracted using 0.8 microl of n-octanol from the headspace of a 2 ml sample solution. The effect of sampling volume, solvent volume, sample temperature, syringe plunger withdrawal rate and ionic strength of the solution on the extraction performance were studied. A semiautomated system including a variable speed stirring motor was used to ensure a uniform movement of syringe plunger through the barrel. The method provided a fairly good precision for all compounds (5.5-9.3%), except methanol (16.4%). Detection limits were found to be between 1 and 97 microg/l within an extraction time of approximately 9.5 min under GC-MS in full scan mode.     

Rapid determination of panaxynol in a traditional Chinese medicine of Saposhnikovia divaricata by pressurized hot water extraction followed by liquid-phase microextraction and gas chromatography-mass spectrometry

Panaxynol is a bioactive component in traditional Chinese medicines (TCMs), such as Saposhnikovia divaricata and Panax ginseng. In the work, two solvent-free sample techniques of pressurized hot water extraction (PHWE) and headspace liquid-phase microextraction (HS-LPME) were combined and developed for the determination of panaxynol in a TCM of S. divaricata. Panaxynol in the TCM samples from different growing areas was extracted by PHWE in dynamic mode, followed by extraction and concentration with HS-LPME and analysis with gas chromatography-mass spectrometry (GC-MS). The PHWE and HS-LPME parameters were optimized and the method validations were studied. Panaxynol in S. divaricata from four different growing areas was quantitatively analyzed by internal standard method. These results have shown that PHWE-LPME-GC-MS is a simple, rapid, efficient and low-cost method for the determination of panaxynol in TCMs and is a potential tool for TCM quality assessment.     

Determination of parabens in wastewater samples via robot-assisted dynamic single-drop microextraction and liquid chromatography–tandem mass spectrometry

Dynamic single-drop microextraction (SDME) was automatized employing an Arduino-based lab-made Cartesian robot and implemented to determine parabens in wastewater samples in combination with liquid chromatography–tandem mass spectrometry. A dedicated Arduino sketch controls the auto-performance of all the stages of the SDME process, including syringe filling, drop exposition, solvent recycling, and extract collection. Univariate and multivariate experiments investigated the main variables affecting the SDME performance, including robot-dependent and additional operational parameters. Under selected conditions, limit of detections were established at 0.3 µg/L for all the analytes, and the method provided linear responses in the range between 0.6 and 10 µg/L, with adequate reproducibility, measured as intraday relative standard deviations (RSDs) between 5.54% and 17.94%, (n = 6), and inter-days RSDs between 8.97% and 16.49% (n = 9). The robot-assisted technique eased the control of dynamic SDME, making the process more feasible, robust, and reliable so that the developed setup demonstrated to be a competitive strategy for the automated extraction of organic pollutants from water samples.     

Oxidation of 2-dialkylaminomethyl-4,6-di-tert-butylphenols

Oxidative transformations of 2-dialkylaminomethyl-4,6-di-tert-butylphenols depend on the nature of the oxidant, the character of the substituents at the nitrogen atom, and the medium. A mechanism of the oxidation of these compounds is suggested. The molecular structure of the compound obtained as a result of oxidative trimerization of 2-dimethylaminomethyl-4,6-di-tert-butylphenol was established by X-ray structural analysis. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1328–1335, July, 1997.     

四氯化碳液相催化加氢制氯仿多元金属催化剂的制备及其催化性能

以贵金属M(=Pd,Pt)为主要活性成分,掺加过渡金属Fe和Ni作为助剂,采取浸渍和氢气还原法制备了椰壳活性炭(ACcs)负载的单元金属(M/ACcs)、二元金属(M-Ni/ACcs、M-Fe/ACcs)和三元金属(M-Ni-Fe/ACcs)系列催化剂;通过CC_l4液相催化加氢制氯仿反应考察了这些催化剂的催化活性和选择性。结果表明,Pd基催化剂的催化活性明显高于Pt基催化剂,但后者对氯仿的选择性优于前者;在前5 h加氢反应时段,两系列催化剂的活性顺序为:Pd-Ni-Fe/ACcsPd-Fe/ACcsPd/ACcsPd-Ni/ACcs和Pt/ACcs≈Pt-Fe/ACcsPt-Ni/ACcsPt-Ni-Fe/ACcs;总体上,引入Fe对于催化性能的改善效果要优于Ni,Ni的单独引入则会不同程度地降低催化活性。综合考量成本、活性和选择性等因素,优选Pd-Ni-Fe/ACcs作为催化剂,在393 K下反应5 h,可实现CC_l497.6%的转化率以及接近100%氯仿的选择性。     

Intermetallic Compounds: Liquid-Phase Synthesis and Electrocatalytic Applications

Characterized by long-range atomic ordering, well-defined stoichiometry, and controlled crystal structure, intermetallics have attracted increasing attention in the area of chemical synthesis and catalytic applications. Liquid-phase synthesis of intermetallics has arisen as the promising methodology due to its precise control over size, shape, and resistance toward sintering compared with the traditional metallurgy. This short review tends to provide perspectives on the liquid-phase synthesis of intermetallics in terms of both thermodynamics and methodology, as well as its applications in various catalytic reactions. Specifically, basic thermodynamics and kinetics in the synthesis of intermetallics will be first discussed, followed by discussing the main factors that will affect the formation of intermetallics during synthesis. The application of intermetallics in electrocatalysis will be demonstrated case by case at last. We conclude the review with perspectives on the future developments with respect to both synthesis and catalytic applications.     

Driving Organic Nanocrystals Dissolution Through Electrochemistry

We have recently discussed how organic nanocrystal dissolution appears in different morphologies and the role of the solution pH in the crystal detriment process. We also highlighted the role of the local molecular chemistry in porphyrin nanocrystals having comparable structures: in water-based acid solutions, protonation of free-base porphyrin molecules is the driving force for crystal dissolution, whereas metal (Zn^II) porphyrin nanocrystals remain unperturbed. However, all porphyrin types, having an electron rich π-structure, can be electrochemically oxidized. In this scenario, a key question is: does electrochemistry represent a viable strategy to drive the dissolution of both free-base and metal porphyrin nanocrystals? In this work, by exploiting electrochemical atomic force microscopy (EC-AFM), we monitor in situ and in real time the dissolution of both free-base and metal porphyrin nanocrystals, as soon as molecules reach the oxidation potential, showing different regimes according to the applied EC potential.     

金属有机骨架材料在吸附分离研究中的应用进展

作为一种新型的纳米多孔材料,金属有机骨架材料（Metal-Organic Frameworks,MOFs）在近二十余年中得到了飞速的发展.MOFs材料由无机金属离子和有机配体通过自组装形成,具有许多优于传统多孔材料的特性.超高的比表面积、较高的孔隙率、可调的孔道尺寸、良好的热稳定性和化学稳定性使得MOFs材料在多个领域中展现出了广阔的应用前景.随着研究的不断深入,MOFs材料被广泛应用于催化反应、吸附分离、生物医学等领域中,并表现出了优异的效果.本文着力于近年来MOFs材料在吸附分离研究中的进展,重点介绍了这类材料在能源气体贮存、碳捕获、膜分离、液相吸附、色谱的分离净化方面的应用,并对其今后的发展进行了展望.     

Co_3O_4/BiOI复合催化剂的制备及其光催化性能

考察了两种方法制备的BiOI光催化剂,结果显示溶剂热法制备的BiOI比液相沉淀法制备的BiOI具有更好的光催化活性.然后,以溶剂热法制备的BiOI采用浸渍法制备了CoOx/BiOI复合催化剂,用X射线衍射(XRD)、紫外-可见(UV-vis)漫反射光谱、透射电子显微镜(TEM)等手段对其进行了表征,探讨了煅烧温度,煅烧时间以及Co掺杂量对其光催化性能的影响.结果显示:在300℃煅烧2h,Co的掺杂量为2.0%(Co/BiOI)的条件下,CoOx/BiOI复合物紫外光催化活性最高.结构研究表明,Co是以Co3O4的形式呈针状分布在团聚后的BiOI的表面,这有效地促进了BiOI的光催化性能.