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181.
Abhishek Maurya Arun Kumar Mahato Nikita Chaudhary Neha Kesharwani Payal Kachhap Vivek Kumar Mishra Chanchal Haldar 《应用有机金属化学》2020,34(4):e5508
Two vanadium (IV) complexes [VIVO(Haeae-sal)(MeOH)]+ ( 1 ) and [VIVO(Haeae-hyap)(MeOH)]+ ( 2 ) were prepared by reacting [VO(acac)2] with ligands [H2aeae-sal] ( I ) and [H2aeae-hyap] ( II ) respectively. Condensation of 2-(2-aminoethylamino)ethanol with salicylaldehyde and 2-hydroxyacetophenone produces the ligands ( I ) and ( II ) respectively. Both vanadium complexes 1 and 2 are sensitive towards aerial oxygen in solution and rapidly convert into vanadium(V) dioxido species. Vanadium(V) dioxido species crystalizes as the dimeric form in the solid-state. Single-crystal XRD analysis suggests octahedral geometry around each vanadium center in the solid-state. To access the benefits of heterogeneous catalysis, vanadium(V) dioxido complexes were anchored into the polymeric chain of chloromethylated polystyrene. All the synthesized neat and supported vanadium complexes have been studied by a number of techniques to confirm their structural and functional properties. Bromoperoxidase activity of the synthesized vanadium(V) dioxido complexes 3 and 4 was examined by carrying out oxidative bromination of salicylaldehyde and oxidation of thioanisole. In the presence of hydrogen peroxide, 3 shows 94.4% conversion ( TOF value of 2.739 × 102 h−1) and 4 exhibits 79.0% conversion (TOF value of 2.403 × 102 h−1) for the oxidative bromination of salicylaldehyde where 5-bromosalicylaldehyde appears as the major product. Catalysts 3 and 4 also efficiently catalyze the oxidation of thioanisole in the presence of hydrogen peroxide where sulfoxide is observed as the major product. Covalent attachment of neat catalysts 3 and 4 into the polymer chain enhances substrate conversion (%) and their catalytic efficiency increases many folds, both in the oxidative bromination and oxidation of thioether. Polymer supported catalysts 5 displayed 98.8% conversion with a TOF value of 1.127 × 104 h−1 whereas catalyst 6 showed 95.7% conversion with a TOF value of 4.675 × 103 h−1 for the oxidative bromination of salicylaldehyde. These TOF values are the highest among the supported vanadium catalysts available in the literature for the oxidative bromination of salicylaldehyde. 相似文献
182.
We present a facile and efficient method for modifying the surface of silica-coated Fe3O4 magnetic nanoparticles (MNPs) with bis(pyrazolyl) triazine ruthenium(II) complex [ MNPs@BPT–Ru (II) ] . Field emission-scanning electron microscopy, thermogravimetric/derivative thermogravimetry analysis, X-ray powder diffraction, Fourier-transform infrared spectroscopy, vibrating sample magnetometry, and energy-dispersive X-ray spectrometry analyses were employed for characterizing the structure of these nanoparticles. MNPs@BPT–Ru(II) nanoparticles proved to be a magnetic, reusable, and heterogeneous catalyst for the hydrogen transfer reduction of ketone derivatives. In addition, highly pure products were obtained with excellent yields in relatively short times in the presence of this catalyst. A comparison of this catalyst with those previously used for the hydrogen transfer reactions proved the uniqueness of MNPs@BPT–Ru(II) nanoparticle which is due to its inherent magnetic properties and large surface area. The presented method also had other advantages such as simple reaction conditions, eco-friendliness, high recovery ability, easy work-up, and low cost. 相似文献
183.
The objective of this research work was to investigate the kinetics of esterification of acetic acid with n-butanol through the variation of experimental parameters. The reaction mixture was catalyzed heterogeneously by a sulfonated catalyst in batch mode of operation. The catalyst was prepared from abundantly available agro-waste, Cajanus cajan husk by chemical activation process, which produces a carbon-based solid catalyst with high surface area. The catalyst was characterized by a Brunauer-Emmet-Teller surface analyzer and Fourier transform infrared spectroscopy to know the surface morphology. Process parameters such as contact time, reaction temperature, and catalyst loading, which can influence the extent of conversion of reactants, were studied. Furthermore, the kinetic investigation was also carried out to estimate the kinetic parameters for uncatalyzed and catalyzed reaction using the second-order pseudo-homogeneous (P-H), Eley-Rideal (E-R), and Langmuir-Hinshelwood (LH) kinetic models for this research work. The kinetic parameters such as activation energy, preexponential factor, and the thermodynamic parameters such as enthalpy and entropy were estimated for uncatalyzed and catalyzed reactions using these three models. The process conditions were optimized for catalyzed and uncatalyzed reactions to obtain the maximum product yield by minimizing root mean square error of each experimental data using the MS-excel solver tool. Thus, this study reveals the high potential of an agro-waste, Cajanus cajan husk as raw material for the synthesis of catalyst. The results show that the E-R model is more appropriate for predicting the dynamic data of an esterification reaction, as the forward rate of reaction estimated using the E-R model are more modified than P-H and L-H models. 相似文献
184.
合理布置的滑移/非滑移异质界面可以提高流体动压润滑性能,但目前滑移区和非滑移区的组合方式大多采用单一的直线拼接法,没有针对流体润滑摩擦副的各类工况设计出相应的优化方案,为此本文建立了一组离散式二次方程来描述滑移区和非滑移区拼接轨迹,并引入计算域单元的宽长比作为优化变量,分别以液膜刚度和摩擦因数作为优化目标,通过MATLAB数值仿真求解不同宽长比条件下滑移区和非滑移区的最优拼接轨迹。结果表明,与直线拼接法相比,选取二次方程所描述的抛物线作为滑移区和非滑移区拼接轨迹的方法使流体润滑摩擦副在摩擦因数和液膜刚度等性能指标上都有所改善,而且根据不同的优化目标参数可以方便地绘制出最优拼接方案,验证了本文方法在改善动压润滑性能上的可行性和普适性。 相似文献
185.
The new inorganic–organic hybrids based on SO3H‐functionalized ionic liquids (ILs) and Keggin‐type heteropoly acids (H3PW12O40, H3PMo12O40, and H4SiW12O40; HPAs) are prepared and characterized by FT‐IR, NMR, XRD, CV, SEM/EDX, ICP‐OES, BJH and UV. Different molecular structures according to the different inorganic part were also proved. Potentiometric titration showed a good relationship between catalytic activity and acidity of the catalysts. Electrochemical aspects showed electron transfer ability of the compounds. For understanding catalytic activities of the HPA‐IL hybrids in N‐formylation reaction, effect of catalyst composition, substrate, and reaction conditions were studied. The best SO3H‐functionalized ionic liquid catalyst was readily recovered and reused for four runs. Easy preparation of the catalyst, simple and easy work‐up, mild reaction conditions, low cost, excellent yields and short reaction times are the key features of this work. 相似文献
186.
For the first time, intensification of monooleoyl glycerol (MOG) synthesis has been investigated in an ultrasonic-infrared-wave (USIRW) promoted batch reactor. Esterification of octadecanoic acid (ODA) with glycerol (Gl) has been conducted [using Amberlyst 36 wet catalyst] in three different reactors, namely traditional batch reactor (TBR), infrared wave promoted batch reactor (IRWPBR), and USIRW-promoted batch reactor (USIRWPBR) to assess the relative efficacy. The energy-efficient USIRWPBR remarkably intensifies the ODA-Gl esterification as manifested through superior ODA conversion (92.5 ± 1.25%) compared to that achieved in IRWPBR (79.8 ± 1.2%) and TBR (36.39 ± 1.25%). The most favorable reaction condition for optimum ODA conversion and maximum MOG yield was identified through statistical optimization over a selected parametric range, namely 3-5 Gl/ODA mole ratio, 0.004-0.006 g/mL Amberlyst 36 catalyst concentration, 300-700 rpm impeller speed, and 333-353 K reaction temperature. The present study also reports the formulation and validation of an innovative reaction kinetics, that is, concurrent noncatalytic and heterogeneously catalyzed (CNCHC) reaction mechanism in addition to the conventional heterogeneous kinetic models (LH and Eley-Rideal mechanisms). Under combined USIRW, the CNCHC esterification mechanism could best describe ODA-Gl esterification (R2 = 0.98) compared to LH (R2 = 0.97) and Eley-Rideal (R2 = 0.88) mechanisms. The optimal product (MOG) was characterized by differential scanning calorimetry and thermogravimetric analysis to assess its crystallization property and thermal stability for possible application as plasticizer/fuel additives. 相似文献
187.
Niloufar Afzali Reihaneh Kardanpour Farnaz Zadehahmadi Shahram Tangestaninejad Majid Moghadam Valiollah Mirkhani Adam Mechler Iraj Mohammadpoor‐Baltork Mehrnaz Bahadori 《应用有机金属化学》2019,33(11)
A novel heterogeneous nanocatalyst was established by supporting molybdenum (VI) on Zr6 nodes in the structure of the well‐known UiO‐66 metal–organic framework (MOF). The structure of the UiO‐66 before and after Mo (VI) immobilization was confirmed with XRD, DR‐FTIR and UV–vis spectroscopy, and the presence and amount of Mo (VI) was identified by X‐ray photoelectron spectroscopy and inductively coupled plasma atomic emission spectroscopy. TEM imaging confirmed the absence of Mo clusters on the MOF surface, while SEM confirmed that the appearance of the MOF has not changed upon immobilizing the Mo (VI) catalyst. BET adsorption measurements were used to confirm the porosity of the catalyst. The catalytic activity of this heterogeneous catalyst was investigated in oxidation of sulfides with H2O2 in acetonitrile and oxidative desulfurization of dibenzothiophene. Easy work up, convenient and steady reuse and high activity and selectivity are prominent properties of this new hybrid material. 相似文献
188.
选取黄骅坳陷新近系典型辫状河沉积解剖区,利用密井网区动静态资料相结合识别和刻画心滩及其内部结构,在此基础上通过沉积数值模拟探究研究区心滩形成过程,并建立研究区心滩顺流迁移和横向迁移演化模式。结果表明:顺流加积、垂向加积、侧向加积和侵蚀作用共同塑造心滩的形态和内部结构;滩头侵蚀、滩尾顺流加积和垂向加积形成了心滩的顺流生长和垂向生长;侧向加积与侵蚀作用控制心滩的不对称侧向生长过程。 相似文献
189.
《Mendeleev Communications》2022,32(4):510-513
The influence of textural characteristics on the catalytic performance of supported KCoMoS2 catalysts was explored to provide essential information for the design of better catalysts for the synthesis of higher alcohols (C1–C5) from syngas. Syngas conversion was carried out over KCoMoS2 catalysts supported on various mesoporous (alumina and carbon-coated alumina) and microporous (two types of powdered activated carbons) materials. The experimental results show that catalysts supported over microporous materials exhibit higher catalytic activity in HAS from syngas than catalysts based on mesoporous materials. 相似文献
190.
Synchronizing Substrate Activation Rates in Multicomponent Reactions with Metal–Organic Framework Catalysts
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Dr. Lina María Aguirre‐Díaz Dr. Marta Iglesias Dr. Natalia Snejko Prof. Enrique Gutiérrez‐Puebla Prof. M. Ángeles Monge 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(19):6654-6665
A study on the influence of the cation coordination number, number of Lewis acid centers, concurrent existence of Lewis base sites, and structure topology on the catalytic activity of six new indium MOFs, has been carried out for multicomponent reactions (MCRs). The new indium polymeric frameworks, namely [In8(OH)6(popha)6(H2O)4]?3 H2O ( InPF‐16 ), [In(popha)(2,2′‐bipy)]?3 H2O ( InPF‐17 ), [In3(OH)3(popha)2(4,4′‐bipy)]?4 H2O ( InPF‐18 ), [In2(popha)2(4,4′‐bipy)2]?3 H2O ( InPF‐19 ), [In(OH)(Hpopha)]?0.5 (1,7‐phen) ( InPF‐20 ), and [In(popha)(1,10‐phen)]?4 H2O ( InPF‐21 ) (InPF=indium polymeric framework, H3popha=5‐(4‐carboxy‐2‐nitrophenoxy)isophthalic acid, phen=phenanthroline, bipy=bipyridine), have been hydrothermally obtained by using both conventional heating (CH) and microwave (MW) procedures. These indium frameworks show efficient Lewis acid behavior for the solvent‐free cyanosilylation of carbonyl compounds, the one pot Passerini 3‐component (P‐3CR) and the Ugi 4‐component (U‐4CR) reactions. In addition, InPF‐17 was found to be a highly reactive, recyclable, and environmentally benign catalyst, which allows the efficient synthesis of α‐aminoacyl amides. The relationship between the Lewis base/acid active site and the catalytic performance is explained by the 2D seven‐coordinated indium framework of the catalyst InPF‐17 . This study is an attempt to highlight the main structural and synthetic factors that have to be taken into account when planning a new, effective MOF‐based heterogeneous catalyst for multicomponent reactions. 相似文献