Oxidation Of Ethylbenzene Research Articles

Cr-Containing Rare-Earth Substituted Yttrium Iron Garnet Ferrites: Catalytic Properties in the Ethylbenzene Oxidation

A series of the Cr-containing erbium substituted yttrium iron garnet ferrites (ECYIG) was synthesized with distinct Cr amounts, herein referred to as Y3(Er0.02Fe5Cr1−x)O12, where x refers to Cr amounts from 0 to 0.05. The catalytic performance of the solids was investigated in ethylbenzene oxidation in the presence of hydrogen peroxide to assess the role of Cr and Er present in the YIG garnet lattice for fine chemistry compound production. Raman spectroscopy, HRTEM, EPR and FTIR revealed that the insertion of Er (at a fixed amount of 2%) in dodecahedral sites had a great impact on the catalytic activity of the garnets. Both Er3+ and Y3+ in the lattice simultaneously provided structural stability to the garnet structure in any harsh environment. XPS and EPR indicated that the Cr3+ ions replaced those of Fe3+ located in both octahedral and tetrahedral sites of the YIG garnets. The Cr3+ ions acted as electronic promoter to increase the oxidation rate of the Fe3+ active species responsible for activating the EB molecule. SEM-EDS demonstrated that the solids having Cr amounts lower than 4% experienced the most severe deactivation due to the Cr leaching and strong carbon species adsorption on the surface of the catalysts, which decreased their efficiency in the reaction.

Synthesis of Nitrogen-doped Carbon Supported Cerium Single Atom Catalyst by Ball Milling for Selective Oxidation of Ethylbenzene

Synthesis of Nitrogen-doped Carbon Supported Cerium Single Atom Catalyst by Ball Milling for Selective Oxidation of Ethylbenzene

Catalyst Performance of the Calcined Products of CoAl Layered Double Hydroxide in the Aerobic Oxidation of Ethylbenzene

Catalyst Performance of the Calcined Products of CoAl Layered Double Hydroxide in the Aerobic Oxidation of Ethylbenzene

Super-paramagnetic polymer composite-supported dendrimer–Mn catalyst: Fabrication, characterization and catalytic evaluation in selective aerobic oxidation of ethylbenzene and oximes derivatives

Design of strategy and catalytic for oxidation ethylbenzene, toxic petroleum, to high value-added via hydrogen-atom-transfer process is lately attracting a renewed interest from both environmentally and economic view. Herein, novel manganese-based dendritic catalysts supported on the polymer-magnetic core-shell were synthesized, fully identified and evaluated with initiator NDHPI for selective and easy-to-handle aerobic oxidation of ethylbenzene (EB) and oximes to acetophenone (ACP) & carbonyl compounds (AH/KO), respectively. Besides mild condition reaction, the supported dendrimer-encapsulated Mn NPs also exhibited outstanding catalytic performance, such as selective oxidation of ethylbenzene and oximes using O2 as green and cheaper oxidant with excellent reactivity, selectivity, stability, and magnetic recyclability. Additionally, the effect of operating parameters such as the amount of catalyst, nature of solvent, temperature and reaction time, and role of several N-hydroxyimides were studied in the catalytic efficiency of the synthesized dendritic catalyst. The results illustrated that the enhanced catalytic efficiency of the catalyst is derived from the magnetic dendritic structures, high Mn(II) content, hydrophobic arm of dendrimers, and interaction of Mn and the dendritic framework. Finally, the reaction pathway for EB and oxime has been deduced, and the crucial role of dendritic catalyst, NDPHI, and electronic effect has been elucidated.

A Unique Fe-N4 Coordination System Enabling Transformation of Oxygen into Superoxide for Photocatalytic CH Activation with High Efficiency and Selectivity.

Selective oxidation of CH bonds is one of the most important reactions in organic synthesis. However, activation of the α-CH bond of ethylbenzene by use of photocatalysis-generated superoxide anions (O2 •- ) remains a challenge. Herein, the formation of individual Fe atoms on polymeric carbon nitride (CN), that activates O2 to create O2 •- for facilitating the reaction of ethylbenzene to form acetophenone, is demonstrated. By utilizing density functional theory and materials characterization techniques, it is shown that individual Fe atoms are coordinated to four N atoms of CN and the resultant low-spin Fe-N4 system (t2g 6 eg 0 ) is not only a great adsorption site for oxygen molecules, but also allows for fast transfer of electrons generated in the CN framework to adsorbed O2 , producing O2 •- . The oxidation reaction of ethylbenzene triggered by O2 •- ions turns out to have a high conversion rate of 99% as well as an acetophenone selectivity of 99%, which can be ascribed to a novel reaction pathway that is different from the conventional route involving hydroxyl radicals and the production of phenethyl alcohol. Furthermore, it possesses great potential for other CH activation reactions besides ethylbenzene oxidation.

The Dual Function of PhOH Included in the Coordination Sphere of the Nickel Complexes in the Processes of Oxidation with Dioxygen.

The role of ligands in the regulation of the catalytic activity of Ni-complexes (Ni(acac)2) in green process-selective ethylbenzene oxidation with O2 into α-phenyl ethyl hydroperoxide is considered in this article. The dual function of phenol (PhOH) included in the coordination sphere of the nickel complex as an antioxidant or catalyst depends on the ligand environment of the metal. The role of intermolecular H-bonds and supramolecular structures (AFM method) in the mechanisms of selective catalysis by nickel complexes in chemical and biological oxidation reactions is analyzed.

Assessing Peroxygenase-Mediated Oxidations in the Presence of High Concentrations of Water-Miscible Co-Solvents

The use of water-miscible organic co-solvents in biocatalysis is a simple procedure for obtaining higher enzymatic activities toward hydrophobic substrates. However, effects on activity and stability have to be carefully evaluated, also with regard to the type and concentration of the respective co-solvent. In this contribution, we investigated and evaluated the effect of some common water-miscible co-solvents on the biocatalytic performance of the recombinant unspecific peroxygenase rAaeUPO from Agrocybe aegerita. rAaeUPO showed promising activities in the presence of high concentrations of the best co-solvent acetonitrile, which enabled to use higher substrate concentrations (≥100 mM). Employing high acetonitrile concentrations for UPO-mediated oxidation of ethylbenzene to (R)-1-phenylethanol was demonstrated under preparative scale conditions and led to product accumulation rates of 31 mM h−1.

Unveiling the highly disordered NbO6 units as electron-transfer sites in Nb2O5 photocatalysis with N-hydroxyphthalimide under visible light irradiation

Although different NbOx units are present in Nb2O5-based catalysts, the correlations between these structures and activity remain unclear, which considerably hinders the further development of Nb2O5 photocatalysis. Herein, we utilized N-hydroxyphthalimide (NHPI) as the probe molecule to distinguish the role of different NbOx units in the activation of C–H bond under visible light irradiation. With the addition of NHPI, Nb2O5 catalysts with highly disordered NbO6 units exhibited higher activities than that with slightly disordered NbO6 units (419–495 vs. 82 μmol·g−1·h−1) in photocatalytic selective oxidation of ethylbenzene. Revealed by Raman spectra, electron paramagnetic resonance spectra, and transmission-electron-microscopy images, highly disordered NbO6 units were confirmed to act as the active sites for the transfer of photogenerated electrons from NHPI, promoting the generation of phthalimide-N-oxyl (PINO) radicals for the enhanced conversion of ethylbenzene under visible light irradiation. This study provides guidance on the role of local NbOx units in Nb2O5 photocatalysis.

Simultaneous oxidation of aromatic compounds using Sr‐doped lanthanum manganites as catalysts

Strontium-doped lanthanum manganites, La1-xSrxMnO3 (LSMO), are promising and affordable catalysts for oxidative degradation of volatile organic compounds. LSMO catalysts (x = 0, .1, .2, and .3) were prepared by the citrate-nitrate autocombustion (CNA) and coprecipitation synthesis. The phase composition was confirmed by X-ray diffraction and Rietveld refinement analysis, while the oxygen content was determined by Mohr's salt permanganate titration. Morphology and porosity of prepared catalysts was correlated to catalytic oxidation of benzene, toluene, ethylbenzene and o-xylene. It was observed that both synthesis methods yielded catalysts of similar average pore size diameter and specific surface area, but the pore size distribution differed: CNA-prepared catalysts had a multimodal pore size distribution, while the coprecipitated ones had a single maximum at 4 nm. Catalysts prepared by the CNA method have shown a higher catalytic activity in the temperature range 373–723 K, as the presence of Mn3+/Mn4+ mixed valences increased their reducibility.

Antioxidant Activity of Diatomic Phenols

Nine compounds are studied for antioxidant activity, including those from the class of catecholamines containing 3,4-hydroxyphenyl (catechol) as a common structural fragment, which imparts antioxidant properties to the compounds in the reactions of hydrocarbon substrate oxidation. The antiradical activity is determined by the chemiluminescent method by the interception of peroxyl radicals in the model reaction of the initiated oxidation of ethylbenzene (RH). The mechanism of the inhibition of chain oxidation processes by diatomic phenol compounds is provided by the presence of two active hydroxy groups with a possible intramolecular hydrogen bond, leading to a weakening of the О–Н bond and a high rate constant of hydrogen abstraction in the reaction with peroxyl radicals (kinh). This reaction is dominant and determines the inhibitory activity of antioxidants in oxidation processes. The maximum inhibitory activity is shown by 3,5- and 3,6-di-tert-butylpyrocatechins, dopamine, and epicatechin.

Reactivity of Cetophenone and Its Derivatives with Semi-Empirise Methods Parameterizedmodel 6 (PM6)

Cetophenone is used as an intermediate in the synthesis of flavones. In industry, Cetophenone is obtained as a by-product of the oxidation of ethyl benzene. The method used for modeling Cetophenone derivatives is a semi-empirical method using (PM6). The cetophenone derivative which has a larger energy difference is found in the compound 2-aceyiylisophyhaloitrile. The highest value of electronegativity and chemical hardness was found in the compound 2-aceyiylisophyhaloitrile and the greatest potential energy value was found in the compound 2-aceyiylisophyhaloitrile.

Promoted selective oxidation of ethylbenzene in liquid phase achieved by hollow CeVO4 microspheres

Herein, we developed a series of CeVO4 samples with hierarchical hollow microsphere-like structure obtained at different calcination temperatures for the selective oxidation of ethylbenzene (EB) to acetophenone (AcPO) in the presence of TBHP. The optimized catalyst (CVO-500) exhibits a very high yield value of 95.0% (initial reaction rate of 49.4 mmol gcat–1 h−1) under the optimal reaction conditions. Importantly, the representative CVO-500 catalyst presents high stability, with the reaction performance well maintained after five consecutive uses. It has been indicated that the redox V5+/V3+ sites serve as the main active centers, while the electronic interaction and redox transformation between Ce and V facilitates the hopping of V5+/V3+ and the generation of oxygen vacancies. The bimetallic synergy between V and Ce thus endows the CVO-500 catalyst an excellent performance in the EB oxidation reaction. This work paves the way for the exploit of high-performance and cost-effective catalyst for the EB oxidation and beyond.

Catalytic activity of ethylbenzene with product selectivity by gold nanoparticles supported on zinc oxide.

The oxidation of ethylbenzene (EB) using tert-butyl hydroperoxide as the oxidizing agent was carried out in presence of gold nanoparticles (3 nm) supported on zinc oxide in acetonitrile solution. A higher selectivity towards acetophenone (ACP) as the major product, and a moderate selectivity towards other products such as 1-phenylethanol (PE), benzaldehyde (BZL), and benzoic acid (BzA) were observed using the prepared Au/ZnO nanocatalysts at 100 °C for 24 h. It is suggested the reaction produces an intermediate product, which is dimethylethyl-1-phenylethyl peroxide through a radical mechanism. A small amount of benzaldehyde was observed because benzaldehyde went autoxidation to form benzoic acid with the presence of oxidation agent of TBHP during reaction. The factors affecting the catalytic activity such as gold loading, calcination treatment at 300°C, type of solvent, reaction time, reaction temperature, oxidant to substrate molar ratio, catalyst weight, and solvent volume were studied. The gold nanoparticle catalyst synthesized by deposition precipitation method using urea was characterized by XRD, HRTEM, ATR-IR, XRF, and BET and offers a very selective reaction pathway for the oxidation of ethylbenzene.

Multistep protection strategy for preparation of atomically dispersed Fe–N catalysts for selective oxidation of ethylbenzene to acetophenone

Atomically dispersed Fe atoms on three-dimensional N-doped hollow carbon spheres single-atom catalyst was prepared, which exhibit excellent catalytic performance for the catalytic oxidation of ethylbenzene under mild reaction conditions.

Nitrogen-doped 3D hollow carbon spheres for efficient selective oxidation of C–H bonds under mild conditions

Nitrogen-doped hollow mesoporous carbon spheres present excellent conversion and selectivity in the selective oxidation of ethylbenzene at 50 °C.

Selective C-H Oxidation of Ethylbenzene to Acetophenone Using Cobalt Phosphine Oxide Complexes

Selective C-H Oxidation of Ethylbenzene to Acetophenone Using Cobalt Phosphine Oxide Complexes

Size effect of Co–N–C-functionalized mesoporous silica hollow nanoreactors on the catalytic performance for the selective oxidation of ethylbenzene

Only the nanoreactor with suitable void size can achieve an ideal balance between enrichment and diffusion and display superior catalytic performance.

Confined Cobalt on Carbon Nanotubes in Solvent‐free Aerobic Oxidation of Ethylbenzene: Enhanced Interfacial Charge Transfer

AbstractAerobic oxidation of hydrocarbons yielding corresponding oxygenated products is one of the most important chemical processes. In current work, carbon nanotubes supported encapsulated cobalt nanoparticles with carbon layers (Co@C/CNTs) were synthesized and utilized as catalysts in the oxidation of ethylbenzene (EB) in the liquid phase, exhibiting high catalytic performance. The synergistic effect between Co@C and CNTs played the vital role on facilitating the decomposition of peroxides to enhance the overall activity. The inadequate covered Co@C on CNTs surface were considered as catalytic sites. Density functional theory revealed that the exist of Co nanoparticles could improve the interaction between the catalyst and intermediate free radicals, which were significant for EB oxidation. Last but not least, the electron transfer on carbon surface was enhanced by the incorporation of Co@C nanoparticles, which greatly improved the catalytic performance on EB oxidation. This study provides a new insight into the Co‐based catalysts in the aerobic oxidation of hydrocarbons.

Ethyl benzene oxidation under aerobic conditions using cobalt oxide imbedded in nitrogen-doped carbon fiber felt wrapped by spiral TiO2-SiO2

Carbon fiber felt (CFF) as a carbonaceous framework has received great attention in catalysis applications. In this work, a novel nanocomposite composed of cobalt oxide micro-sized particles (MPs) incorporated in nitrogen-doped carbon and wrapped by coil-like TiO2-SiO2 layer was fabricated through a co-assembly protocol including MPs implanting, hydrolysis and calcination steps. The structural properties and performance of the prepared Co/N-CFF@TiO2-SiO2 catalyst was evaluated by different techniques. Mechanical, chemical and thermal stabilities of CFF were stepwise improved and the results explain how the N-CFF matrix and strong spiral envelope promoted textural features in the final composite. Moreover, the catalyst exhibited good activity in oxidation of ethyl benzene by molecular oxygen. Under optimized conditions (130 °C, 12 h, 5 mL of ethylbenzene, 20 bar O2 pressure), the ethyl benzene conversion and acetophenone selectivity were 25% and 88%, respectively. The novel Co/N-CFF@TiO2-SiO2 catalyst showed excellent long-term stability over 6 consecutive cycles, which permits to consider it as an ideal platform for application at industrial scales due to its green and bulk nature.

Impact of As-Prepared and Purifıed Multi-Walled Carbon Nanotubeson the Liquid-Phase Aerobic Oxidatıon of Hydrocarbons

The article presents simple kinetic approaches to study the effect of multi-walled carbon nanotubes (MWCNTs) additives on the aerobic oxidation of hydrocarbons and to propose real acceptable mechanisms of the process. The aerobic liquid phase low-temperature oxidation of ethylbenzene conducted in the presence of multi-walled carbon nanotubes has been used as a model pattern. Kinetic analysis established the catalytic action associated with the presence of the iron compounds in inner channels of MWCNTs. These compounds are identified as ferric carbides provoking decomposition of the ethylbenzene hydroperoxide and thereby suppressing the competitive route of alky-peroxide radicals addition to the nanocarbon cage. Thus the reaction finally proceeds in the autocatalytic mode.Contradictory conclusions on the effect of CNTs on the oxidation chain processes existing in the literature are associated with the lack of control over nature and content of metal impurities in channels of nanotubes.