Catalysts For Epoxidation Research Articles

Zeolite Y-based catalysts for efficient epoxidation of R-(+)-Limonene: Insights into the structure-activity relationship

Parent, hierarchical, and metal-modified hierarchical zeolite Y were investigated as heterogeneous catalysts in the R-(+)-limonene epoxidation, a catalytic route for synthesizing precursors of bio-polycarbonates, an alternative to isocyanate polyurethanes. The fresh catalysts underwent detailed characterization using XRD, N2 physisorption, TEM, SEM-EDX, pyridine-FTIR, NH3-TPD, CO2-TPD, UV–Vis-DRS, and solid-state NMR. Spent materials were investigated by TPO-MS and TGA, confirming low coke formation on the catalytic surface. The most active material was K–Sn-modified dealuminated zeolite Y, reflected in a high turnover frequency (TOF) of 96 h−1. This material exhibited the lowest Brønsted to Lewis acidity ratio (0.1), the highest mesoporosity fraction (43%), and the lowest total surface area (465 m2 g−1). Aprotic polar solvents with high polarity and medium donor capacity appeared suitable for limonene epoxidation. Limonene conversion of ca. 97% was reached at 70 °C, H2O2: limonene molar ratio = 7, and acetonitrile as a solvent, while selectivity to total monoepoxides exhibited values up to 96% under different reaction conditions. Hydration of internal epoxides to limonene diol was favored at high temperatures and high H2O2/limonene molar ratios. The efficiency of H2O2 reached maximum values of about 85% at low H2O2 amounts, while no significant influence was observed for temperature, catalyst amount, and the initial concentration of limonene. A plausible reaction mechanism was proposed for the R-(+)-limonene epoxidation with H2O2 based on the experimental findings.

Cobalt Supported on Ce-MOF-Derived CeO2 as a Catalyst for the Efficient Epoxidation of Styrene Under Aerobic Conditions

Cobalt Supported on Ce-MOF-Derived CeO2 as a Catalyst for the Efficient Epoxidation of Styrene Under Aerobic Conditions

Mechanism of the Sharpless Epoxidation Reaction: A DFT Study.

The Sharpless reaction is an enantioselective epoxidation of prochiral allylic alcohols that employs a Ti(IV) catalyst formed from titanium tetra(isopropoxide), Ti(O-i-Pr)4, diethyl tartrate (DET), and the oxidizing agent tert-butyl hydroperoxide. The M06-2X DFT functional with the 6-311+G(d,p) basis set has been employed to model the structures and energetics of the Sharpless epoxidation reaction. The monomeric tetracoordinate titanium(IV) diethyltartrate is thermodynamically strongly favored to dimerize, producing a pentacoordinate catalyst, [Ti(DET)(O-i-Pr)2]2, that is a more reactive chiral epoxidation catalyst. The rapid ligand exchange reactions needed to generate the "loaded" catalyst and to repeat the overall catalytic cycle have been examined and are found to have activation energies that are much lower than the epoxidation barriers. The transition structures and activation energies for the enantioselective epoxidation of allyl alcohol, trans-methyl-allyl alcohol and trans-tert-butyl-allyl alcohol with the "loaded" Sharpless catalyst, [Ti2(DET)2(O-i-Pr)2-(OAllyl)-(OOt-Bu)], are presented. The effect of the C═O···Ti interactions on the activation energies and the significance of the O-C-C═C dihedral angle on the enantioselectivity of the epoxidation reaction are discussed.

Tracking Coordination Environment and Reaction Intermediates in Homogeneous and Heterogeneous Epoxidation Catalysts via Ti L2,3-Edge Near-Edge X-ray Absorption Fine Structures.

Ti-based molecules and materials are ubiquitous and play a major role in both homogeneous and heterogeneous catalytic processes. Understanding the electronic structures of their active sites (oxidation state, local symmetry, and ligand environment) is key to developing molecular-level structure-property relationships. In that context, X-ray absorption spectroscopy (XAS) offers a unique combination of elemental selectivity and sensitivity to local symmetry. Commonly, for early transition metals such as Ti, K-edge XAS is applied for in situ characterization and subsequent structural analysis with high sensitivity toward tetrahedral species. Ti L2,3-edge spectroscopy is in principle complementary and offers specific opportunities to interrogate the electronic structure of five-and six-coordinated species. It is, however, much more rarely implemented because the use of soft X-rays implies ultrahigh vacuum conditions. Furthermore, the interpretation of the data can be challenging. Here, we show how Ti L2,3-edge spectroscopy can help to obtain unique information about both homogeneous and heterogeneous epoxidation catalysts and develop a molecular-level relationship between spectroscopic signatures and electronic structures. Toward this goal, we first establish a spectral library of molecular Ti reference compounds, comprising various coordination environments with mono- and dimeric Ti species having O, N, and Cl ligands. We next implemented a computational methodology based on multiplet ligand field theory and maximally localized Wannier orbitals benchmarked on our library to understand Ti L2,3-edge spectroscopic signatures. We finally used this approach to track and predict the spectra of catalytically relevant intermediates, focusing on Ti-based olefin epoxidation catalysts.

Synthesis, Structural and Redox Properties of Vanadyl β‐Cyanoporphyrin and its Utilization as Efficient Catalyst for Epoxidation of Olefins and Oxidative Bromination of Phenols

Abstract2‐Cyano‐5,10,15,20‐tetraphenylporphyrin [H2TPPCN] (1) having cyano group at one of β‐pyrrolic positions using nucleophilic substitution reaction of tetrabutylammonium cyanide (TBACN) on free‐base 2‐nitro‐5,10,15,20‐tetraphenylporphyrin, and its oxidovanadium(IV) complex [VIVOTPPCN] (2) were synthesized in good yields. Both the porphyrins 1 and 2 have been characterized by UV‐Vis spectroscopy, mass spectrometry, and cyclic voltammetric techniques. Single crystal X‐Ray crystallography revealed quasi‐planar geometry for 1. Compounds 1 and 2 exhibited a red shift (λmax=7–9 nm) in the Soret band relative to [MTPP], where M=2H, VIVO owing to the electron‐withdrawing effect of the cyano group at the β‐position. The first oxidation (ΔE1/2=110–140 mV) and reduction potentials (ΔE1/2=220–260 mV) of 1 and 2 are anodically shifted relative to [MTPP] where M=2H, VIVO. Porphyrin 2 has been utilized as a catalyst for two reactions: epoxidation of olefins and bromination of phenols. The bromination of phenol using KBr/H2O2/HClO4 in water resulted in 100 % conversion with a TOF value as high as 19.6 s−1 in 0.5 h. Using H2O2/NaHCO3 in a CH3CN/H2O solvent mixture at 60 °C, epoxidation was carried out, and the highest conversion rate with a turnover frequency of 1.9 s−1 was achieved in the case of cyclohexene. Catalyst 2 was recovered successfully at the end of the reaction up to 5 cycles and had good thermal stability, indicating its industrial viability and applicability. Moreover, these cyano‐functionalized porphyrins could be further utilized for the generation of molecular self‐assemblies, post‐functionalization of porphyrin core and various applications. The current findings in this work present insights for a facile approach for the synthesis of β‐cyano functionalized porphyrin 1 and further shed light on the utility of its vanadyl complex 2 as an efficient catalyst for olefin epoxidation and phenol bromination reactions.

Epoxidation of Olefins Catalyzed by Sulfate‐based Supramolecular Ion Pairs

AbstractThe development of inexpensive and effective catalysts for the epoxidation of olefins to epoxides, which are key commodities for the chemical industry, is a continuing challenge. In this context, we present a supramolecular solution with the development of new host‐guest assemblies of sulfate ions and amidoammonium receptor cations that, for the first time, are shown to act as catalysts for olefin epoxidation by hydrogen peroxide under biphasic conditions. Analysis of the reaction mechanism shows that the reactive and oxidizing peroxymonosulfate is formed in the organic phase. Furthermore, a variety of readily available precursors may be used to form the supramolecular ion pairs (SIPs), which is enabling a large‐scale synthesis of the catalysts while maintaining catalytic control and effectiveness.

Preparative and Catalytic Properties of MoVI Mononuclear and Metallosupramolecular Coordination Assemblies Bearing Hydrazonato Ligands.

A series of polynuclear, dinuclear, and mononuclear Mo(VI) complexes were synthesized with the hydrazonato ligands derived from 5-methoxysalicylaldehyde and the corresponding hydrazides (isonicotinic hydrazide (H2L1), nicotinic hydrazide (H2L2), 2-aminobenzhydrazide (H2L3), or 4-aminobenzhydrazide (H2L4)). The metallosupramolecular compounds obtained from non-coordinating solvents, [MoO2(L1,2)]n (1 and 2) and [MoO2(L3,4)]2 (3 and 4), formed infinite structures and metallacycles, respectively. By blocking two coordination sites with cis-dioxo ligands, the molybdenum centers have three coordination sites occupied by the ONO donor atoms from the rigid hydrazone ligands and one by the N atom of pyridyl or amine-functionalized ligand subcomponents from the neighboring Mo building units. The reaction in methanol afforded the mononuclear analogs [MoO2(L1-4)(MeOH)] (1a-4a) with additional monodentate MeOH ligands. All isolated complexes were tested as catalysts for cyclooctene epoxidation using tert-butyl hydroperoxide (TBHP) as an oxidant in water. The impact of the structure and ligand lability on the catalytic efficiency in homogeneous cyclooctene epoxidation was elucidated based on theoretical considerations. Thus, dinuclear assemblies exhibited better catalytic activity than mononuclear or polynuclear complexes.

Construction of a highly stable natural silicate-supported molybdenum catalyst for efficient epoxidation of olefins

Epoxides are important bulk chemicals, playing irreplaceable role in the chemical industry, but facing serious pollution and low productivity in the production process. Therefore, the development of green and efficient epoxidation of olefins by stable catalysts with low prices is of great significance. In this study, a Mo-MATP catalyst was prepared by modifying Mo(CO)₆ on attapulgite through Si-O bonding. Mo-MATP exhibits excellent performance (99% yield of cyclooctane oxide, CYCO) and stability (80% selectivity of CYCO after 17 cycles), highly tert-butyl hydroperoxide (TBHP) utilization, and extensive substrate scalability. Furthermore, the in-situ Fourier Transform Infrared Spectroscopy (FT-IR), Electron Spin-resonance Spectroscopy (ESR) and High Resolution Mass Spectrometry (HRMS) spectra suggest that TBHP would be activated by Mo-MATP to generate peroxyl radicals, which then oxidize alkenes to their corresponding epoxides. In this study, the stable loading of Mo would largely solve the problem of Mo loss during the catalytic process, thus providing a stable and dispersed Mo active center, enabling the catalyst to possess high catalytic performance and recycling stability.

Enhancing Catalytic Efficiency in Long-Chain Linear α-Olefin Epoxidation: A Study of CaSnO3-Based Catalysts

This investigation explores the synthesis of advanced catalysts for epoxidizing long-chain linear α-olefins, a pivotal process in the chemical industry for generating critical intermediates. Employing a hydrothermal technique, we developed four distinct catalysts (CS-1–4), methodically modulating the Ca/Sn ratio to elucidate its impact on the catalysts’ physicochemical properties. Our research uncovered that an escalated Ca/Sn ratio induces a morphological shift from octagonal to cubic structures, concomitant with a diminution in particle size and an enhancement in specific surface area. Significantly, the CS-3 catalyst outperformed others in 1-octene epoxidation, an efficacy attributed to its augmented surface alkalinity and proliferation of medium-strength alkaline sites, likely emanating from increased surface oxygen defects. Subsequent hydrogen reduction of CS-3 further amplified these oxygen defects, yielding a 10% uptick in catalytic activity. This correlation underscores the potential of oxygen defect manipulation in optimizing catalytic efficiency. Our findings contribute a novel perspective to the development of robust, high-performance catalysts for α-olefin epoxidation, seamlessly aligning with the principles of sustainable chemistry.

Trifluoromethyl Ketone Galactose Catalyst for Asymmetric Epoxidation: Experimental and Theoretical Model

AbstractSince the introduction of the Shi catalyst, the organocatalytic epoxidation of olefins has become an area of continued research interest. To explore the possibility of enhancing the efficiency and stability of the catalyst, the synthesis of a galactose‐derived trifluoromethyl ketone, and its use for stereoselective epoxidation reaction that exploits a transitory dioxirane as active species are herein reported. The trifluoromethyl ketone was built on the C6 of a protected d‐galactopyranose. The organocatalyst was obtained smoothly in a few steps, and when utilized for stereoselective epoxidation exhibited excellent stability as no chemical alterations were observed during the reaction. The stereoselectivity, although sometimes moderate, appears surprisingly high considering the conformational freedom of the trifluoromethyl ketone moiety.DFT calculations were performed to investigate the interactions involved in regulating the observed selectivities. Moreover, a new mnemonic model has been developed to serve as a fast‐predicting tool for epoxidation of new substrates.

Fabrication of gold nanoparticles supported on hollow microsphere of nanosized TS-1 for the epoxidation of propylene with H2 and O2

The TS-1 microsphere was facilely prepared via a direct spray drying of the mixture containing the nanocrystal TS-1 and mother liquor. The calcined TS-1 zeolites possess a hollow structure and numerous intercrystalline mesopores, which may facilitate the diffusion properties. Au nanoparticles were loaded on TS-1 support by utilizing a deposition–precipitation process to prepare the Au/TS-1-M catalysts for propylene epoxidation in the presence of H2 and O2 conditions. The effects of the Ti and Au loadings on the structure, porosity, morphology, and catalytic performances of the Au/TS-1 catalysts have been investigated by various techniques. Under the optimized synthesis conditions (Si/Ti molar ratio = 57, 0.49 wt% Au), a propylene conversion of 6.1 % and a PO selectivity of 91.7 % were obtained on the Au/TS-1 catalyst. A PO formation rate of 186.8 gPO·kgcat.−1·h−1 was achieved at the 20th hour.

Titanium dioxide functionalized silicon carbide phases as heterogeneous epoxidation catalysts.

We report silicon carbide (SiC) based epoxidation catalysts constituted of a silicon carbide core and a silica/titania (SiO2/TiO2) shell. The catalysts were obtained via surface modification of SiC microparticles and were used as heterogeneous catalysts for the epoxidation of cyclohexene using tert-butyl hydroperoxide or cumyl hydroperoxide as the oxidant. Conversions up to 83% and selectivities of more than 90% were obtained.

Thermocatalytic epoxidation by cobalt sulfide inspired by the material's electrocatalytic activity for oxygen evolution reaction.

New discoveries in catalysis by earth-abundant materials can be guided by leveraging knowledge across two sub-disciplines of heterogeneous catalysis: electrocatalysis and thermocatalysis. Cobalt sulfide has been reported to be a highly active electrocatalyst for the oxygen evolution reaction (OER). Under these oxidative conditions, cobalt sulfide forms oxidized surfaces that outperform directly prepared cobalt oxide in OER catalysis. We postulated that the catalytic activity of oxidized cobalt sulfide for OER could reflect a more general ability to catalyze O-transfer reactions. Herein, we show that cobalt sulfide (CoS x ) indeed catalyzes the epoxidation of cyclooctene, a thermal O-transfer reaction. Similarly to OER, the surface-oxidized CoS x formed under reaction conditions outperformed the directly prepared cobalt oxide, hydroxide, and oxyhydroxide for epoxidation catalysis. Another notable phenomenological parallel to OER was revealed by the electron paramagnetic resonance (EPR) analysis of all spent Co-based catalysts that showed significant structural changes and the formation of paramagnetic Co(ii) and Co(iv) species. Mechanistic investigations suggest that a higher density of Co(ii) and/or an easier formation of high-valent Co species in the case of surface-oxidized cobalt sulfide is responsible for its high activity as an epoxidation catalyst. Our results provide important insight into the surface chemistry of Co-based catalysts and show the potential of oxidized CoS x as an earth-abundant catalyst for O-transfer reactivity beyond OER. This work highlights the utility of bridging electrocatalysis and thermocatalysis for the development of more sustainable chemical processes.

A cobalt(II) coordination polymer-derived catalyst engineered via temperature-induced semi-reversible single-crystal-to-single-crystal (SCSC) dehydration for efficient liquid-phase epoxidation of olefins.

Single-crystal-to-single-crystal (SCSC) transformations provide more avenues for phase transitions, which have piqued great interest in crystal engineering. In this work, a 3D Co(II)-based coordination polymer (CP), {Co2(OH2)8(btec)}·4H2O (1), (where (btec)4- = 1,2,4,5-benzenetetracarboxylate) undergoes SCSC transition upon heating at 180 °C to afford an anhydrous phase [Co2(btec)] (1'). Room-temperature water-vapour induced semi-reversible SCSC transformation of 1' involves condensation of two water molecules coordinating to the metal cluster, yielding a new framework [Co2(OH2)2(btec)] (2). These SCSC transitions were accomplished through a sequential bond breaking and new bond formation process which was accompanied by colour changes from orange (1) → violet (1') → pink (2). All materials were structurally elucidated by single-crystal X-ray diffraction (SCXRD) and further established by various analytical techniques. According to SCXRD data, all the frameworks possess octahedral geometries around the cobalt(II) sphere. SCXRD studies further revealed that 1 is a polymeric architecture with a binodal 4-c sql topology while 1' and 2 possess (3,6)-c kgd and (4,6)-c scu 3D nets, respectively. By virtue of multitopicity exhibited by the tetracarboxylate, the coordination number of the linker around the Co(II) sphere increased from four (in 1) to eight (in 1') and then decreased to six (in 2). Most interestingly, permanent porosity could be observed for the dihydrate 2, originated from potential void space as substantiated by dinitrogen (N2) sorption isotherm. These porous frameworks were active catalysts for the aerobic epoxidation of the model substrate cyclohexene using molecular oxygen (O2) as the final oxidant in the presence of the sacrificial i-butyraldehyde (IBA) reductant. For using the dihydrous phase 2, cyclohexene and various other olefins were catalytically oxidised to their corresponding epoxides with up to 38.5% conversion and 99.0% selectivity. The catalyst 2 can be expediently recycled in four runs without significant loss of activity. This research demonstrates that a little innovation in the active-site-engineered organic-inorganic hybrid materials can significantly enhance the catalytic performance and selectivity of coordination polymer-derived heterogeneous catalysts.

Development of a Ru-porphyrin-based supramolecular framework catalyst for styrene epoxidation.

A new microporous supramolecular-framework Ru(II)-porphyrin catalyst containing non-covalent interactions between pyrenylphenyl moieties at the meso-position of the porphyrin ring is synthesised and structurally characterised. This recyclable catalyst expedites styrene epoxidation more efficiently than homogeneous Ru-porphyrin catalytic systems.

Insight into the influence of Re and Cl on Ag catalysts in ethylene epoxidation

Crystalline AgReO4 was formed in Re-promoted Ag catalysts. The effect of Re on catalysis and EO isomerization was tested without and with the industrially relevant ethyl chloride. EO isomerization was greatly affected by both Re and Cl.

Mechano-synthesis of a AgSrFeO3 catalyst for epoxidation of ethylene in a chemical looping set-up

The catalyst AgSrFeO3(imp), used in chemical looping epoxidation of ethylene-to-ethylene oxide (EtO), is usually synthesised via a conventional impregnation method.

A novel Ag-loaded 4 Å zeolite as an efficient catalyst for epoxidation of styrene.

In this study, a novel Ag-loaded 4 Å zeolite was synthesized through the combined action of strong ultrasound and a high-voltage electrostatic field (the Z-Ag-UE) and its catalytic activity was evaluated in the epoxidation of styrene. The prepared catalysts were characterized using XRD, SEM, XPS, BET, TG, ICP-OES. The results showed that the silver evenly dispersed inside the octahedral 4 Å zeolite structure rather than being attached to the surface of the material like in the impregnation method, and this Ag-loaded 4 Å zeolite had a high surface area, uniform particle size distribution, and excellent high temperature thermal stability. The catalytic performance of the Ag-loaded 4 Å zeolite was investigated by varying the reaction conditions such as the amount of catalyst, temperature, and reaction time. Under optimized conditions, the Ag-loaded 4 Å zeolite showed high selectivity and conversion for the epoxidation of styrene, achieving a conversion rate of up to 98% and a selectivity of 94%. In particular, the catalyst had excellent recyclability and was reused more than fifteen times with the catalytic performance remaining unchanged. This method of loading metal prepared under external field conditions provides a new method and idea for future research in related fields.

Chiral imidazolium and triazolium salts as NHC and aNHC ligand precursors: A promising framework for asymmetric epoxidation catalysis

Two chiral imidazolium salts and one chiral triazolium salt were synthesized containing a chiral cyclohexane bridge based on the salen ligand framework of the Jacobsen-Katsuki epoxidation catalysts. They are promising NHC and aNHC ligand precursors for asymmetric epoxidation or C–H oxidation catalyzed by organometallic compounds. The ligand framework offers plenty of opportunities for modification.

Bulky olefin epoxidation under mild conditions over Mo-based oxide catalysts

Epoxidation of bulky olefins, such as biobased fatty acid methyl esters (FAMEs), with tert-butylhydroperoxide (TBHP), under mild conditions, was promoted by nanocatalysts possessing Mo and M = Ta, Nb or W, prepared via simple, versatile methodology.