Formation of Al2(MoO4)3 on MoO3/$gamma;-Al2O3 catalyst systems as studied by luminescence spectroscopy

In recent years, numerous researchers have focused on the development of catalytic methods for processing of biomass-derived sugars into alkyl lactates, which are widely used as non-toxic solvents and are the starting material for obtaining monomeric lactide. In this work, the transformation of fructose into methyl lactate on Sn-containing catalyst in the flow reactor that may be of practical interest was studied. The supported Sn-containing catalyst was ob-tained by a simple impregnation method of granular γ-Al2O3. The catalytic ex-periments were performed in a flow reactor at temperatures of 160-190 °C and pressure of 3.0 MPa. The 1.6-9.5 wt.% fructose solutions in 80% aqueous methanol were used as a reaction mixture. It was found that addition to a reac-tion mixture of 0.03 wt.% potassium carbonate leads to the increase in selec-tivity towards methyl lactate on 15% at 100% conversion of fructose. Prod-ucts of the target reaction С6Н12О6 + 2СН3ОН = 2С4Н8О3 + 2Н2О were ana-lyzed using 13C NMR method. The following process conditions for obtaining of 65 mol% methyl lactate yield at 100% fructose conversion were found: use of 4.8 wt.% fructose solution in 80% methanol, 180 °С, 3.0 МПа and a load on catalyst 1.5 mmol C6H12O6/mlcat/h at contact time of 11 minutes. The cata-lyst productivity is 2.0 mmol C4H8O3/mlcat/h and the by-productі are 1,3-dihydroxyacetone dimethyl acetal (20%) and 5-hydroxymethylfurfural (10%). It should be noted that a racemic mixture of L- and D-methyl lactates has been obtained by conversion of D-fructose on the SnO2/Al2O3 catalyst. The SnO2/Al2O3 catalyst was found to be stable for 6 h while maintaining full fruc-tose conversion at 55–70% methyl lactate selectivity. After regeneration the catalyst completely restores the initial activity.

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Kinetics of reverse water-gas shift reaction over CuO/ZnO/Al2O3 catalyst

Catalysis in Green Chemistry and Engineering ◽

10.1615/catalgreenchemeng.2020036423 ◽

2020 ◽

Author(s):

Suhas Jadhav ◽

Prakash Vaidya

Keyword(s):

Water Gas Shift ◽

Water Gas Shift Reaction ◽

Reverse Water Gas Shift ◽

Shift Reaction ◽

Water Gas ◽

Kinetics Of ◽

Al2o3 Catalyst

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Computationally-Guided Investigation of Dual Amine/pi Lewis Acid Catalysts for Direct Additions of Aldehydes and Ketones to Unactivated Alkenes and Alkynes

10.26434/chemrxiv.7538114.v2 ◽

2020 ◽

Author(s):

Eric Greve ◽

Jacob D. Porter ◽

Chris Dockendorff

Keyword(s):

Lewis Acid ◽

Density Functional ◽

Acid Catalyst ◽

Metal Catalyst ◽

Catalyst Poisoning ◽

Lewis Acid Catalysts ◽

Metal Ligands ◽

Aldehydes And Ketones ◽

Lewis Acid Catalyst ◽

Catalyst Systems

Dual amine/pi Lewis acid catalyst systems have been reported for intramolecular direct additions of aldehydes/ketones to unactivated alkynes and occasionally alkenes, but related intermolecular reactions are rare and not presently of significant synthetic utility, likely due to undesired coordination of enamine intermediates to the metal catalyst. We reasoned that bulky metal ligands and bulky amine catalysts could minimize catalyst poisoning and could facilitate certain examples of direct intermolecular additions of aldehyde/ketones to alkenes/alkynes. Density Functional Theory (DFT) calculations were performed that suggested that PyBOX-Pt(II) catalysts for alkene/alkyne activation could be combined with MacMillan’s imidazolidinone organocatalyst for aldehyde/ketone activation to facilitate desirable C-C bond formations, and certain reactions were calculated to be more exergonic than catalyst poisoning pathways. As calculated, preformed enamines generated from the MacMillan imidazolidinone did not displace ethylene from a biscationic (t-Bu)PyBOX-Pt2+complex, but neither were the desired C-C bond formations observed under several different conditions.

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Computationally-Guided Investigation of Dual Amine/pi Lewis Acid Catalysts for Direct Additions of Aldehydes and Ketones to Unactivated Alkenes and Alkynes

10.26434/chemrxiv.7538114 ◽

2020 ◽

Author(s):

Eric Greve ◽

Jacob D. Porter ◽

Chris Dockendorff

Keyword(s):

Lewis Acid ◽

Density Functional ◽

Acid Catalyst ◽

Metal Catalyst ◽

Catalyst Poisoning ◽

Lewis Acid Catalysts ◽

Metal Ligands ◽

Aldehydes And Ketones ◽

Lewis Acid Catalyst ◽

Catalyst Systems

Dual amine/pi Lewis acid catalyst systems have been reported for intramolecular direct additions of aldehydes/ketones to unactivated alkynes and occasionally alkenes, but related intermolecular reactions are rare and not presently of significant synthetic utility, likely due to undesired coordination of enamine intermediates to the metal catalyst. We reasoned that bulky metal ligands and bulky amine catalysts could minimize catalyst poisoning and could facilitate certain examples of direct intermolecular additions of aldehyde/ketones to alkenes/alkynes. Density Functional Theory (DFT) calculations were performed that suggested that PyBOX-Pt(II) catalysts for alkene/alkyne activation could be combined with MacMillan’s imidazolidinone organocatalyst for aldehyde/ketone activation to facilitate desirable C-C bond formations, and certain reactions were calculated to be more exergonic than catalyst poisoning pathways. As calculated, preformed enamines generated from the MacMillan imidazolidinone did not displace ethylene from a biscationic (t-Bu)PyBOX-Pt2+complex, but neither were the desired C-C bond formations observed under several different conditions.

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A New Computational Interface for Catalysis

10.26434/chemrxiv.8040737.v4 ◽

2019 ◽

Author(s):

Pavlo Kravchenko ◽

Craig Plaisance ◽

David Hibbitts

Keyword(s):

Zeolite Catalyst ◽

Metal Ceramic ◽

Catalyst Systems ◽

Computational Catalysis

This manuscript outlines the utility and power of our computational catalysis interface. This interface has been developed by our group and used extensively to study metal, ceramic, and zeolite catalyst systems.

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Employing Exfoliated Graphite as Novel Support Material for Heterogeneous Model Catalysts

10.26434/chemrxiv.8079620 ◽

2019 ◽

Author(s):

Moritz Wolf ◽

Nico Fischer ◽

Michael Claeys

Keyword(s):

Surface Area ◽

Graphite Powder ◽

Model Catalysts ◽

Model Systems ◽

Exfoliated Graphite ◽

Support Material ◽

Heterogeneous Model ◽

Support Materials ◽

Metal Support Interaction ◽

Catalyst Systems

The inert nature of graphitic samples allows for characterisation of rather isolated supported nanoparticles in model catalysts, as long as sufficiently large inter-particle distances are obtained. However, the low surface area of graphite and the little interaction with nanoparticles result in a challenging application of conventional preparation routes in practice. In the present study, a set of graphitic carbon materials was characterised in order to identify potential support materials for the preparation of model catalyst systems. Various sizes of well-defined Co3O4 nanoparticles were synthesised separately and supported onto exfoliated graphite powder, that is graphite after solvent-assisted exfoliation via ultrasonication resulting in thinner flakes with increased specific surface area. The developed model catalysts are ideally suited for sintering studies of isolated nano-sized cobaltous particles as the graphitic support material does not provide distinct metal-support interaction. Furthermore, the differently sized cobaltous particles in the various model systems render possible studies on structural dependencies of activity, selectivity, and deactivation in cobalt oxide or cobalt catalysed reactions.

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Dimethyldisulphide Hydrodesulphurization on NiCoMo / Al2O3 Catalyst

Revista de Chimie ◽

10.37358/rc.17.7.5703 ◽

2017 ◽

Vol 68 (7) ◽

pp. 1496-1500

Author(s):

Rami Doukeh ◽

Mihaela Bombos ◽

Ancuta Trifoi ◽

Minodora Pasare ◽

Ionut Banu ◽

...

Keyword(s):

Good Accuracy ◽

Fixed Bed ◽

Continuous System ◽

Space Velocity ◽

Molar Ratio ◽

Catalytic Reactor ◽

Liquid Hourly Space Velocity ◽

Hydrodesulfurization Process ◽

Al2o3 Catalyst ◽

Simplified Kinetic Model

Hydrodesulphurization of dimethyldisulphide was performed on Ni-Co-Mo /�-Al2O3 catalyst. The catalyst was characterized by determining the adsorption isotherms, the pore size distribution and the acid strength. Experiments were carried out on a laboratory echipament in continuous system using a fixed bed catalytic reactor at 50-100�C, pressure from 10 barr to 50 barr, the liquid hourly space velocity from 1h-1 to 4h-1 and the molar ratio H2 / dimethyldisulphide 60/1. A simplified kinetic model based on the Langmuir�Hinshelwood theory, for the dimethyldisulphide hydrodesulfurization process of dimethyldisulphide has been proposed. The results show the good accuracy of the model.

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Synthesis of Phosphonates, Phosphinates and Tertiary Phosphine Oxides by Pd- or Ni-Catalyzed Microwave-Assisted P–C Coupling Reactions without the Addition of Conventional Ligands

Current Organic Chemistry ◽

10.2174/1385272825999210101234850 ◽

2021 ◽

Vol 25 ◽

Author(s):

Réka Henyecz ◽

György Keglevich

Keyword(s):

Tautomeric Form ◽

Catalyst Precursor ◽

Coupling Reactions ◽

Optimum Conditions ◽

Pd Catalysts ◽

Catalyst Complex ◽

Two Factors ◽

Dialkyl Phosphites ◽

Catalyst Systems ◽

P Ligands

Abstract: Microwave (MW)-assistance may be a powerful tool also in the Hirao P–C coupling reactions of vinyl/aryl halides with dialkyl phosphites in the presence of Pd-catalysts/P-ligands elaborated forty years ago. This review surveys the development of this reaction by showing the expansion of the reagents and catalysts, as well as the information accumulated. The stress was laid on the “green” aspects, the simplification of the catalyst systems, and the reliable mechanistic details in order to be able to establish the optimum conditions. The best protocol involves the use of some excess of the >P(O)H reagent to ensure the PdII→Pd0 reduction and, via its trivalent tautomeric form (>POH) also the P-ligand. The overall rate is the result of two factors, the activity of the catalyst complex formed, and the reactivity of the reactants in the P–C coupling reactions. Both components are influenced by the nature of the aryl substituents in Ar2P(O)H. NiII salts may also be used as the catalyst precursor, however, despite the PdII→Pd0→PdII route, in this case, a NiII→NiIV→NiII sequence was proved.

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