Cr2O3-Al2O3 mixed oxide material: synthesis, structure and catalytic behavior for C-H activation

This work reports the synthesis of Cr2O3-Al2O3 mixed oxide material via the sol-gel process. The characterization techniques used are X-ray diffraction, Nitrogen adsorption, scanning Electron Microscopy, UV-visible and FT-IR spectroscopy. The results show the presence of the boehmite phase and it cannot be possible to identify crystalline phase of Cr2O3. The surface BET of Cr2O3-Al2O3 is about 130.5 m2/g. The catalytic behavior of the mesoporous material is evaluated for the liquid- phase oxidation of cyclohexane with hydrogen peroxide as oxidant.  Cr2O3-Al2O3 was shown to be mild and efficient catalyst. The use of acetone as solvent presented an approximate 12.4% conversion with 89.66 % selectivity into cyclohexanol

Catalytic Properties of Alumina-Supported Ruthenium, Platinum, and Cobalt Nanoparticles towards the Oxidation of Cyclohexane to Cyclohexanol and Cyclohexanone

A series of metal-loaded (Ru, Pt, Co) alumina catalysts were evaluated for the catalytic oxidation of cyclohexane using tertbutylhydroperoxide (TBHP) as oxidant and acetonitrile or acetic acid as solvent. These materials were prepared by the impregnation method and then characterized by Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES), H2 chemisorption, Fourier Transformed Infrared Spectroscopy (FTIR), High-Resolution Transmission Electron Microscopy (HRTEM), and X-ray Diffraction (XRD). All the prepared materials acted as efficient catalysts. Among them, Ru/Al2O3 was found to have the best catalytic activity with enhanced cyclohexane conversion of 36 %, selectivity to cyclohexanol and cyclohexanone of 96 % (57.6 mmol), and cyclohexane turnover frequency (TOF) of 288 h-1. Copyright © 2018 BCREC Group. All rights reservedReceived: 26th May 2017; Revised: 17th July 2017; Accepted: 18th July 2017; Available online: 22nd January 2018; Published regularly: 2nd April 2018How to Cite: Rekkab-Hammoumraoui, I., Choukchou-Braham, A. (2018). Catalytic Properties of Alumina-Supported Ruthenium, Platinum, and Cobalt Nanoparticles towards the Oxidation of Cyclohexane to Cyclohexanol and Cyclohexanone. Bulletin of Chemical Reaction Engineering & Catalysis, 13(1): 24-36 (doi:10.9767/bcrec.13.1.1226.24-35)

Ruthenium-doped Titania-pillared Clay for The Selective Catalytic Oxidation of Cyclohexene: Influence of Ru Loading

A series of ruthenium-based catalysts supported on acid-activated montmorillonite (PILC) and interspersed with titanium (Ru/Ti-PILCs) were prepared with various amounts of ruthenium. Their catalytic performances in the selective oxidation of cyclohexene, using tert-butylhydroperoxide (TBHP) as oxidant were checked. The clay structure modification by acid activation and impregnation of transition metals resulted in an enhanced Lewis and Bronsted acidities. The Ru/Ti-PILCs materials were characterized using X-ray diffraction (XRD), surface area and pore volume measurements, surface acidity followed by Fourier transform infrared (FTIR) spectroscopy, chemical analysis, and Scanning Electron Microscopy (SEM). It was found that all catalysts can selectively oxidize cyclohexene through allylic oxidation leading mainly to 2-cyclohexene-1-one (Enone) as the major product, and 2-cyclohexene-1-ol (Enol) as secondary product. With the 5 %Ru/Ti-PILC, it was possible to reach 59 % cyclohexene total conversion, and 87 % selectivity into 2-cyclohexene-1-one and 13 % selectivity into 2-cyclohexene-1-ol.

Contribution a l'etude de catalyseur de type Ziegler utilise en phase liquide. Reaction du triethylaluminium sur des acetylacetonates de metaux de transition

SIGLEINIST T 72909 / INIST-CNRS - Institut de l'Information Scientifique et TechniqueFRFranc

Synthèse et caractérisation des oxydes mixtes type MxOy-TiO2 (M = V, Zr et Si) par voie sol-gel (Application à l'époxydation du cyclohexène)

L'objectif de ce travail est : (i) pour préparer des oxydes mixtes X% MxOy-TiO2 (M = V, Zr et Si), (X = 5, 10, 15 et 20 wt-.% MxOy.) par la méthode sol-gel et suivie par une calcination à 500 C, (ii) de caractériser les échantillons préparés par différentes méthodes d'analyse physico-chimique (AAF, ICP, DRX, BET, TG-DTA et FT-IR) et (iii) d'étudier leur réactivité dans l'époxydation de cyclohexène.D'après les résultats des caractérisations, nous constatons que :- L'analyse DRX montre que pour les trois systèmes nous avons l'apparition de la phase anatase de TiO2. La meilleure cristallinité a été observée pour le système en présence de V2O5. La phase de SiO2 est amorphe et la phase de ZrO2 n'a pas été détectée.- L'analyse par adsorption d'azote, donne le classement de ces systèmes selon leurs surfaces spécifiques comme suit :SiO2-TiO2>ZrO2-TiO2>V2O5-TiO2- L'analyse FT-IR de l'adsorption de la pyridine in situ montre que les trois systèmes présentent des sites acides de Lewis, alors que le 15%V2O5-TiO2 présente en plus les sites de Brönsted.Nous avons étudié aussi l'influence de divers paramètres expérimentaux sur la réaction d'époxydation du cyclohexène. Les résultats des tests catalytiques montrent que :- Les meilleurs résultats sont obtenus pour le système V2O5-TiO2.- Les meilleurs solvants sont l'heptane et l'acétonitrile qui donnent une bonne activité catalytique et une bonne sélectivité en époxyde.- La réaction d'époxydation du cyclohexène est une réaction du second ordre.- Le catalyseur 20% V2O5-TiO2 est stable au cours de la réaction catalytique et recyclable.The aim of this work is: (i) to prepare mixed oxides X%MxOy-TiO2 (M = V, Zr and Si), (X = 5, 10, 15 and 20 wt.-% MxOy) by sol-gel method followed by calcination at 500C, (ii) to characterize the prepared samples by different methods of physicochemical analysis (AAF, ICP, XRD, BET, TG-DTA and FT-IR) and (iii) to study their reactivity in the epoxidation of cyclohexene. According to the characterization results, we found that:- The XRD analysis shows that, for the three systems, TiO2 anatase has been evidenced. The best crystallinity was observed for the V2O5-TiO2 system. The TiO2 rutile phase has been obeserved for sample 5% ZrO2-TiO2, while the SiO2 phase is amorphous and ZrO2 phase was not detected.- Analysis by nitrogen adsorption, gave the sorting of these systems according to their specific surface areas as follows: SiO2-TiO2 > ZrO2-TiO2 > TiO2-V2O5- The FTIR analysis of in situ pyridine adsorption showed that all three systems display Lewis acid sites, whereassample 15% V2O5-TiO2 present Bronsted sites too.We studied the effect of different reaction parameters in the oxidation of cyclohexene. The results of the catalytic tests show that:- The best results are obtained for V2O5-TiO2 system.- The best solvents are heptane and acetonitrile which give good catalytic activity and high epoxide selectivity.- The epoxidation reaction of cyclohexene is a second-order reaction.- The catalyst 20%V2O5-TiO2 is stable during the catalytic reaction and suitable for recycling.POITIERS-SCD-Bib. électronique (861949901) / SudocSudocFranceF

Synthèses, caractérisations et étude de l'acido-basicité d'oxydes mixtes MOx-TIO2 et MOx-AL2O3 (M=Cr, V) (essais de tests catalytiques)

Cette thèse concerne la préparation par voie sol-gel, la caractérisation et l'évaluation des performances catalytiques des oxydes mixtes de type X%MxOy-TiO2, X%MxOy-Al2O3 et X%MxOy-SiO2 avec M = Cr ou V et X = 0, 5, 10 ou 20 %. L'analyse texturale montre bien que ces matériaux présentent un mélange de micropores et de mésopores avec une variation de la surface spécifique, du volume poreux et du diamètre des pores fonction de la teneur du métal ajoutée. L'analyse IR in situ utilisant la pyridine comme molécule sonde révèle la présence des sites acides de Lewis et de Brönsted. Dans le cas des matériaux X%MxOy-TiO2, l'analyse par DRX met en évidence la présence des deux phases anatase et rutile. La transition anatase-rutile dépend de la température de traitement, de la nature et de la quantité du dopant. La présence du chrome retarde cette transition alors que le vanadium l'accélère. L'étude cinétique de cette transition conduit à une transformation du premier ordre avec une énergie d'activation plus grande en présence du vanadium qu'en présence du chrome. Les performances catalytiques de nos matériaux ont été étudiées en oxydation du cyclohexane en phase liquide en présence de H2O2 et du TBHP comme oxydants. L'activité catalytique augmente en fonction de la teneur en chrome. Par contre elle diminue en fonction de la teneur en vanadium. La présence du chrome conduit à une sélectivité plus importante vis-à-vis de la formation de cyclohexanol par rapport à celle de la cyclohexanone. Nous avons étudié aussi l'influence du solvant (acide acétique, acétonitrile et cyclohexane) sur l'activité et la sélectivité. Dans le cas des catalyseurs x%CrxOy-TiO2, l'activité catalytique varie en fonction de la polarité du solvant et de ce fait la conversion varie dans l'ordre suivant : acétonitrile > acide acétique > cyclohexane. Dans le cas des catalyseurs x%VxOy-TiO2, la meilleure activité est obtenue pour l'acide acétique comme solvant et la conversion varie dans l'ordre suivant : acide acétique > cyclohexane > acétonitrile.This thesis deals with the preparation by sol-gel procedure, the characterization and evaluation of catalytic performance of mixed oxide-type X%MxOy-TiO2, X%MxOy-Al2O3 and X%MxOy-SiO2 with M = Cr or V and X = 0, 5, 10 or 20. The textural analysis shows that these materials display a variation of specific surface area, pore volume and pore diameter depending on the content of the metal added. XRD analysis of X%MxOy-TiO2, reveals the presence of two phases namely anatase and rutile. The anatase-rutile transition depends on the temperature treatment, the nature and amount of metallic promoter. The presence of chromium delays this transition whereas vanadium accelerates it. The kinetic study of this transition led to a transformation of the first order with higher activation energy in the presence of vanadium than in the presence of chromium. The catalytic performance of our materials have been evaluated in cyclohexane oxidation in liquid phase, in the presence of H2O2 and TBHP as oxidizers. The activity increases with chromium content whereas it decreases with the vanadium content. The presence of chromium increases the selectivity in cyclohexanol formation vs cyclohexanone. We studied the influence of the solvent (acetic acid, acetonitrile and cyclohexane) on the activity and selectivity. In the case of samples X%CrxOy-TiO2, catalytic activity varies in the following order: acetonitrile > acetic acid > cyclohexane. For X%VxOy-TiO2 catalysts, the best activity is obtained for acetic acid as solvent and conversion varies in the following order: acetic acid > cyclohexane > acetonitrile.POITIERS-BU Sciences (861942102) / SudocSudocFranceF

Natural and Modified Clays for the Removal of Cationic Dye from Water

Research and scientific work continue to develop low-cost treatment processes in terms of improving water quality and environmental protection. Oxide of zinc supported in natural clay is synthesized by impregnated method. The role of this modification is to increase the adsorption capacity of a basic dye (Methylene Blue) compared with calcined and natural clays. These samples are characterized by several analytical methods, X-Ray Diffraction (XRD), Thermogravimetric Analysis/Differential Thermal Analysis (TGA/TDA) and Brunauer, Emmett and Teller (BET) theory. The results show that these clays contain three phases, Sericite 2M1, Clinochlore, quartz and the presence of a new phase for the modified clay named zincite. The measured cation exchange capacity (CEC) is 9 cmolc/kg and the BET analysis shows the increase of surface area for these clays, from 9 to 30 m2 g−1. The findings show also that the impregnated clay has a better affinity than others when the kinetics data were well fitted by the pseudo-second-order. The adsorption capacities calculated using Langmuir equation of MB onto natural, calcined and impregnated clays are 154.0, 139.6 and 158.1 mg/g, respectively. The thermodynamic data showed that the adsorption of MB on these samples were exothermic. From this study, it can be concluded that these clays are efficacious materials for cationic dye removal from wastewater

Liquid phase cyclohexene oxidation over vanadia based catalysts with tert-butyl hydroperoxide: Epoxidation versus allylic oxidation

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