Editorial

Jump to: Research, Review

5 pages, 2773 KiB

Open AccessEditorial

Catalytic Epoxidation Reaction

by Sébastien Leveneur, Pasi Tolvanen and Vincenzo Russo

Catalysts 2024, 14(5), 285; https://doi.org/10.3390/catal14050285 - 23 Apr 2024

Viewed by 272

Abstract

The epoxidation of unsaturated groups is a well-known process [...] Full article

(This article belongs to the Special Issue Catalytic Epoxidation Reaction)

► Show Figures

Figure 1

Research

Jump to: Editorial, Review

22 pages, 4302 KiB

Open AccessArticle

In-Depth Kinetic Modeling and Chemical Analysis for the Epoxidation of Vegetable Oils in a Liquid–Liquid–Solid System

by Yudong Meng, Nasreddine Kebir, Xiaoshuang Cai and Sebastien Leveneur

Catalysts 2023, 13(2), 274; https://doi.org/10.3390/catal13020274 - 26 Jan 2023

Cited by 5 | Viewed by 1415

Abstract

A heterogeneous catalyst for producing epoxidized vegetable oils, an important intermediate in the production of non-isocyanate polyurethanes, is essential for product separation and for decreasing the side-reaction, i.e., ring-opening reaction, via the Prileschajew method. The development of reliable kinetic models considering key variables [...] Read more.

A heterogeneous catalyst for producing epoxidized vegetable oils, an important intermediate in the production of non-isocyanate polyurethanes, is essential for product separation and for decreasing the side-reaction, i.e., ring-opening reaction, via the Prileschajew method. The development of reliable kinetic models considering key variables for both phases and the mass transfer phenomena is missing in the literature. The reaction pathway for the ring-opening reaction is also under debate. Therefore, we studied the kinetics of epoxidation of cottonseed oil by perpropionic acid over the solid acid catalyst amberlite IR-120. An in-depth kinetic model was developed by using Bayesian inference. The reaction pathway for the ring opening was investigated. Propionic acid, a weak acid, allows for a decrease in the oxirane ring-opening side reaction. Full article

(This article belongs to the Special Issue Catalytic Epoxidation Reaction)

► Show Figures

Figure 1

22 pages, 7838 KiB

Open AccessArticle

Post-Synthesis Strategies to Prepare Mesostructured and Hierarchical Silicates for Liquid Phase Catalytic Epoxidation

by Diana M. Gomes, Patrícia Neves, Margarida M. Antunes, António J. S. Fernandes, Martyn Pillinger and Anabela A. Valente

Catalysts 2022, 12(12), 1513; https://doi.org/10.3390/catal12121513 - 25 Nov 2022

Cited by 4 | Viewed by 1159

Abstract

Olefin epoxidation is an important transformation for the chemical valorization of olefins, which may derive from renewable sources or domestic/industrial waste. Different post-synthesis strategies were employed to introduce molybdenum species into mesostructured and hierarchical micro-mesoporous catalysts of the type TUD-1 and BEA, respectively, [...] Read more.

Olefin epoxidation is an important transformation for the chemical valorization of olefins, which may derive from renewable sources or domestic/industrial waste. Different post-synthesis strategies were employed to introduce molybdenum species into mesostructured and hierarchical micro-mesoporous catalysts of the type TUD-1 and BEA, respectively, to confer epoxidation activity for the conversion of relatively bulky olefins (e.g., biobased methyl oleate, DL-limonene) to epoxide products, using tert-butyl hydroperoxide as an oxidant. The influences of (i) the type of metal precursor, (ii) type of post-synthesis impregnation method, (iii) type of support and (iv) top-down versus bottom-up synthesis methodologies were studied to achieve superior catalytic performances. Higher epoxidation activity was achieved for a material prepared via (post-synthesis) incipient wetness impregnation of MoO₂(acac)₂ (acac = acetylacetonate) on (pre-treated) siliceous TUD-1 and calcination; for example, methyl oleate was converted to the corresponding epoxide with 100% selectivity at 89% conversion (70 °C). Catalytic and solid-state characterization studies were conducted to shed light on material stability phenomena. Full article

(This article belongs to the Special Issue Catalytic Epoxidation Reaction)

► Show Figures

Graphical abstract

13 pages, 3798 KiB

Open AccessArticle

Nickel Nanoparticles Decorated on Glucose-Derived Carbon Spheres as a Novel, Non-Palladium Catalyst for Epoxidation of Olefin

by Mosaed S. Alhumaimess

Catalysts 2022, 12(10), 1246; https://doi.org/10.3390/catal12101246 - 16 Oct 2022

Cited by 2 | Viewed by 1452

Abstract

Carbon spheres supporting nickel nanoparticles (NPs), generated by the integration of hydrothermal and microwave irradiation techniques, catalyzed the epoxidation of 1-octene, cyclooctene, styrene, allyl alcohol, and cyclohexene. The average particle sizes of the carbon spheres (CSs) and nickel oxide species immobilized on the [...] Read more.

Carbon spheres supporting nickel nanoparticles (NPs), generated by the integration of hydrothermal and microwave irradiation techniques, catalyzed the epoxidation of 1-octene, cyclooctene, styrene, allyl alcohol, and cyclohexene. The average particle sizes of the carbon spheres (CSs) and nickel oxide species immobilized on the CSs were 240 nm and 26 nm, respectively. The fabricated composites incorporating nickel NPs showed higher activity in the cyclohexene epoxidation process. The cyclohexene conversion was enhanced by raising the Ni loading to 10%. Within 14 h, the cyclohexene conversion had grown to 98%. This robust catalytic activity can be attributed to the efficient distribution of Ni species on the CSs, the facile lowering of the surface, and the development of uniformly nanosized species. The composite exhibited good recyclability across at least five cycles (which is not a simple task involving nickel-nanoparticle-based catalysts that are employed in water), and no nickel species leached into the solution, making the total system environmentally benign and cost-effective. Full article

(This article belongs to the Special Issue Catalytic Epoxidation Reaction)

► Show Figures

Figure 1

31 pages, 29703 KiB

Open AccessFeature PaperEditor’s ChoiceArticle

Mechanistic Details of the Sharpless Epoxidation of Allylic Alcohols—A Combined URVA and Local Mode Study

by Marek Freindorf and Elfi Kraka

Catalysts 2022, 12(7), 789; https://doi.org/10.3390/catal12070789 - 18 Jul 2022

Cited by 4 | Viewed by 3994

Abstract

In this work, we investigated the catalytic effects of a Sharpless dimeric titanium (IV)–tartrate–diester catalyst on the epoxidation of allylalcohol with methyl–hydroperoxide considering four different orientations of the reacting species coordinated at the titanium atom (reactions R1–R4) as well as [...] Read more.

In this work, we investigated the catalytic effects of a Sharpless dimeric titanium (IV)–tartrate–diester catalyst on the epoxidation of allylalcohol with methyl–hydroperoxide considering four different orientations of the reacting species coordinated at the titanium atom (reactions R1–R4) as well as a model for the non-catalyzed reaction (reaction R0). As major analysis tools, we applied the URVA (Unified Reaction Valley Approach) and LMA (Local Mode Analysis), both being based on vibrational spectroscopy and complemented by a QTAIM analysis of the electron density calculated at the DFT level of theory. The energetics of each reaction were recalculated at the DLPNO-CCSD(T) level of theory. The URVA curvature profiles identified the important chemical events of all five reactions as peroxide OO bond cleavage taking place before the TS (i.e., accounting for the energy barrier) and epoxide CO bond formation together with rehybridization of the carbon atoms of the targeted CC double bond after the TS. The energy decomposition into reaction phase contribution phases showed that the major effect of the catalyst is the weakening of the OO bond to be broken and replacement of OH bond breakage in the non-catalyzed reaction by an energetically more favorable TiO bond breakage. LMA performed at all stationary points rounded up the investigation (i) quantifying OO bond weakening of the oxidizing peroxide upon coordination at the metal atom, (ii) showing that a more synchronous formation of the new CO epoxide bonds correlates with smaller bond strength differences between these bonds, and (iii) elucidating the different roles of the three TiO bonds formed between catalyst and reactants and their interplay as orchestrated by the Sharpless catalyst. We hope that this article will inspire the computational community to use URVA complemented with LMA in the future as an efficient mechanistic tool for the optimization and fine-tuning of current Sharpless catalysts and for the design new of catalysts for epoxidation reactions. Full article

(This article belongs to the Special Issue Catalytic Epoxidation Reaction)

► Show Figures

Figure 1

22 pages, 5471 KiB

Open AccessArticle

Alkene Epoxidation and Thioether Oxidation with Hydrogen Peroxide Catalyzed by Mesoporous Zirconium-Silicates

by Irina D. Ivanchikova, Olga V. Zalomaeva, Nataliya V. Maksimchuk, Olga A. Stonkus, Tatiana S. Glazneva, Yurii A. Chesalov, Alexander N. Shmakov, Matteo Guidotti and Oxana A. Kholdeeva

Catalysts 2022, 12(7), 742; https://doi.org/10.3390/catal12070742 - 05 Jul 2022

Cited by 6 | Viewed by 1596

Abstract

Mesoporous zirconium-silicates have been prepared using two different methodologies, evaporation-induced self-assembly and solventless organometallic precursor dry impregnation of commercial SiO₂. The samples were characterized by elemental analysis, XRD, N₂ adsorption, TEM, DRS UV–vis and Raman spectroscopic techniques. The catalytic performance [...] Read more.

Mesoporous zirconium-silicates have been prepared using two different methodologies, evaporation-induced self-assembly and solventless organometallic precursor dry impregnation of commercial SiO₂. The samples were characterized by elemental analysis, XRD, N₂ adsorption, TEM, DRS UV–vis and Raman spectroscopic techniques. The catalytic performance of the Zr-Si catalysts was assessed in the epoxidation of three representative alkenes, cyclohexene, cyclooctene and caryophyllene, as well as in the oxidation of methyl phenyl sulfide using aqueous hydrogen peroxide as a green oxidant, with special attention drawn to the structure/activity relationship and catalyst stability issues. The key factors which affect substrate conversion and epoxide selectivity have been defined. The catalysts with larger contents of oligomeric ZrO₂ species revealed higher activity. The nature of alkene and, in particular, its molecular hindrance is crucial, since the adsorption of the epoxide product is the main factor leading to fast catalyst deactivation. In fact, bulky epoxides do not show this effect. After optimization, the oxidation of caryophyllene gave endocyclic monoepoxide with 77% selectivity at 87% alkene conversion. Methyl phenyl sulfoxide afforded 37% of sulfoxide and 63% of sulfone at 57% sulfide conversion. The nature of catalysis was truly heterogeneous and no Zr leaching was observed. Full article

(This article belongs to the Special Issue Catalytic Epoxidation Reaction)

► Show Figures

Graphical abstract

23 pages, 6661 KiB

Open AccessArticle

Influence of the Support on Propene Oxidation over Gold Catalysts

by Ewoud J. J. de Boed, Bryan J. Folmer, Min Tang, Baira Donoeva and Petra E. de Jongh

Catalysts 2022, 12(3), 327; https://doi.org/10.3390/catal12030327 - 11 Mar 2022

Cited by 4 | Viewed by 2599

Abstract

The epoxidation of propene without forming a substantial amount of byproducts is one of the holy grails of catalysis. Supported Cu, Ag and Au catalysts are studied for this reaction and the activity of the supported metals is generally well understood. On the [...] Read more.

The epoxidation of propene without forming a substantial amount of byproducts is one of the holy grails of catalysis. Supported Cu, Ag and Au catalysts are studied for this reaction and the activity of the supported metals is generally well understood. On the contrary, limited information is available on the influence of the support on the epoxide selectivity. The reaction of propene with equal amounts of hydrogen and oxygen was tested over gold nanoparticles deposited onto CeO₂, TiO₂, WO₃, γ-Al₂O₃, SiO_2, TiO₂-SiO₂ and titanosilicate-1. Several metal oxide supports caused further conversion of the synthesized propene oxide. Strongly acidic supports, such as WO₃ and titanosilicate-1, catalyzed the isomerization of propene oxide towards propanal and acetone. Key factors for achieving high PO selectivity are having inert or neutralized surface sites, a low specific surface and/or a low density of surface -OH groups. This work provides insights and practical guidelines to which metal oxide support properties lead to which products in the reaction of propene in the presence of oxygen and hydrogen over supported gold catalysts. Full article

(This article belongs to the Special Issue Catalytic Epoxidation Reaction)

► Show Figures

Graphical abstract

11 pages, 3354 KiB

Open AccessArticle

Kinetics of Grape Seed Oil Epoxidation in Supercritical CO₂

by Juan Catalá, Jesús Manuel García-Vargas, María Jesús Ramos, Juan Francisco Rodríguez and María Teresa García

Catalysts 2021, 11(12), 1490; https://doi.org/10.3390/catal11121490 - 06 Dec 2021

Cited by 3 | Viewed by 2380

Abstract

The epoxidation of grape seed oil in supercritical CO₂, to the best of our knowledge, has been only superficially described in the literature, apart from a short communication and our own previous published work on the topic. In this work, a [...] Read more.

The epoxidation of grape seed oil in supercritical CO₂, to the best of our knowledge, has been only superficially described in the literature, apart from a short communication and our own previous published work on the topic. In this work, a thorough study of the performance of the supercritical epoxidation of grape seed oil is performed in a wide range of conditions, and the kinetic parameters of the supercritical epoxidation of vegetable oils are reported for the first time in the literature. The experimental work has covered a 40–60 °C temperature range at 150 bar, sampling during a period of 48 h. The nature and extent of the side reactions and secondary products obtained have been evaluated, being hydrolysis products and their oligomerization derivatives the major by-products. Reaction rate constants (10⁻² h⁻¹ order) and activation energy parameters were finally calculated from the experimental conversion and epoxy yield data to establish the effect of temperature on the kinetics of the process. Full article

(This article belongs to the Special Issue Catalytic Epoxidation Reaction)

► Show Figures

Graphical abstract

8 pages, 697 KiB

Open AccessArticle

Catalytic Epoxidation of 3-Carene and Limonene with Aqueous Hydrogen Peroxide, and Selective Synthesis of α-Pinene Epoxide from Turpentine

by Vladislav V. Fomenko, Sergey S. Laev and Nariman F. Salakhutdinov

Catalysts 2021, 11(4), 436; https://doi.org/10.3390/catal11040436 - 29 Mar 2021

Cited by 3 | Viewed by 2961

Abstract

The epoxidation of turpentine (technical α-pinene), 3-carene, and limonene with aqueous hydrogen peroxide was studied in a new catalytic system employing manganese sulfate, salicylic acid, sodium bicarbonate, and acetonitrile, as a polar solvent. The proposed approach makes it possible to carry out a [...] Read more.

The epoxidation of turpentine (technical α-pinene), 3-carene, and limonene with aqueous hydrogen peroxide was studied in a new catalytic system employing manganese sulfate, salicylic acid, sodium bicarbonate, and acetonitrile, as a polar solvent. The proposed approach makes it possible to carry out a “chemical separation” of turpentine components, yielding valuable individual derivatives of monoterpenes without the need to isolate individual monoterpene reagents. Specific methods have been developed for the production of α-pinene epoxide, 3-carene epoxide, limonene diepoxide, as well as for two related compounds: 3-carene-5-one and 3-carene-2,5-dione. Full article

(This article belongs to the Special Issue Catalytic Epoxidation Reaction)

► Show Figures

Scheme 1

9 pages, 2340 KiB

Open AccessArticle

Improvement of Propylene Epoxidation Caused by Silver Plasmon Excitation by UV-LED Irradiation on a Sodium-Modified Silver Catalyst Supported on Strontium Carbonate

by Shigeru Sugiyama, Ikumi Okitsu, Kazuki Hashimoto, Yutaro Maki, Naohiro Shimoda, Akihiro Furube, Yuki Kato and Wataru Ninomiya

Catalysts 2021, 11(3), 398; https://doi.org/10.3390/catal11030398 - 21 Mar 2021

Viewed by 1880

Abstract

The effect that UV-LED irradiation exerted on a sodium-modified silver catalyst supported on strontium carbonate (Ag-Na/SrCO₃) was examined during an epoxidation of propylene to propylene oxide. Based on our previous study, we used Ag(56)-Na(1)/SrCO₃ in this study. The numbers in [...] Read more.

The effect that UV-LED irradiation exerted on a sodium-modified silver catalyst supported on strontium carbonate (Ag-Na/SrCO₃) was examined during an epoxidation of propylene to propylene oxide. Based on our previous study, we used Ag(56)-Na(1)/SrCO₃ in this study. The numbers in parentheses refer to the weight percentage of silver and sodium. Although this catalyst system did not contain typical photocatalysts such as titanium oxide or tungsten oxide, UV-LED irradiation of Ag(56)-Na(1)/SrCO₃ resulted in an evident improvement in the selectivity and yield of propylene oxide. Such an advantageous effect of UV-LED irradiation could not be discussed based on the bandgap used in photocatalysts and, therefore, we proposed a mechanism based on the plasmon excitation of silver, which could be accomplished using the irradiation wavelength of UV-LED to produce electrons. Since the lifespan of these electrons is expected to be short, it is difficult to place them into direct contact with the gas phase of oxygen. Once the generated electrons move to SrCO₃, however, the lifespan is improved, which could allow suitable contact with oxygen in the gas phase to form active oxygen. If the oxygen is active for epoxidation as hydrogen peroxide, this could explain the improvement in activity from UV-LED irradiation. Full article

(This article belongs to the Special Issue Catalytic Epoxidation Reaction)

► Show Figures

Figure 1

Review

Jump to: Editorial, Research

17 pages, 3495 KiB

Open AccessReview

Epoxidation of Terpenes

by Yacoub Mahamat Ahmat, Sara Madadi, Luc Charbonneau and Serge Kaliaguine

Catalysts 2021, 11(7), 847; https://doi.org/10.3390/catal11070847 - 14 Jul 2021

Cited by 21 | Viewed by 5206

Abstract

Terpene epoxides are considered as potential primary intermediates in the synthesis of numerous green polymers including epoxy resins, polycarbonates, nonisocyanate polyurethanes and even some polyamides. In this chapter we describe recent efforts from our group to develop catalytic and noncatalytic processes for terpene [...] Read more.

Terpene epoxides are considered as potential primary intermediates in the synthesis of numerous green polymers including epoxy resins, polycarbonates, nonisocyanate polyurethanes and even some polyamides. In this chapter we describe recent efforts from our group to develop catalytic and noncatalytic processes for terpene epoxidation using a variety of oxidizing agents and process intensification methods. Most experimental tests deal with limonene epoxidation with applicability to some other terpenes also demonstrated. Full article

(This article belongs to the Special Issue Catalytic Epoxidation Reaction)

► Show Figures

Figure 1

23 pages, 2941 KiB

Open AccessFeature PaperReview

The Lord of the Chemical Rings: Catalytic Synthesis of Important Industrial Epoxide Compounds

by Yudong Meng, Francesco Taddeo, Adriana Freites Aguilera, Xiaoshuang Cai, Vincenzo Russo, Pasi Tolvanen and Sébastien Leveneur

Catalysts 2021, 11(7), 765; https://doi.org/10.3390/catal11070765 - 24 Jun 2021

Cited by 35 | Viewed by 5121

Abstract

The epoxidized group, also known as the oxirane group, can be considered as one of the most crucial rings in chemistry. Due to the high ring strain and the polarization of the C–O bond in this three-membered ring, several reactions can be carried [...] Read more.

The epoxidized group, also known as the oxirane group, can be considered as one of the most crucial rings in chemistry. Due to the high ring strain and the polarization of the C–O bond in this three-membered ring, several reactions can be carried out. One can see such a functional group as a crucial intermediate in fuels, polymers, materials, fine chemistry, etc. Literature covering the topic of epoxidation, including the catalytic aspect, is vast. No review articles have been written on the catalytic synthesis of short size, intermediate and macro-molecules to the best of our knowledge. To fill this gap, this manuscript reviews the main catalytic findings for the production of ethylene and propylene oxides, epichlorohydrin and epoxidized vegetable oil. We have selected these three epoxidized molecules because they are the most studied and produced. The following catalytic systems will be considered: homogeneous, heterogeneous and enzymatic catalysis. Full article

(This article belongs to the Special Issue Catalytic Epoxidation Reaction)

► Show Figures

Figure 1

Journal Menu

Journal Browser

Catalytic Epoxidation Reaction

Share This Special Issue

Special Issue Editors

Special Issue Information

Keywords

Published Papers (12 papers)

Editorial

Research

Review

Further Information

Guidelines

MDPI Initiatives

Follow MDPI