Epoxidation Catalysis

A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Catalytic Materials".

Deadline for manuscript submissions: closed (31 December 2018) | Viewed by 17018

Special Issue Editors


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Guest Editor
Department of Chemical Sciences, University of Naples “Federico II”, Via Cinthia, IT-80126, Naples, Italy
Interests: biorefinery; kinetics; chemical reaction engineering; ethoxylation

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Guest Editor
CNR-Istituto di Scienze e Tecnologie Molecolari, Via C. Golgi, 19, 20133 Milano, Italy
Interests: heterogeneous catalysis; inorganic nanosystems applied to catalysis and to synthesis of fine chemicals; sustainable oxidation processes; degradation of hazardous chemicals
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Special Issue Information

Dear Colleagues,

The epoxidation reaction of the C=C double bond is one of the most powerful and versatile tools in synthetic chemistry, from the laboratory level up to the industrial scale. It is used to produce bulk chemicals (i.e., ethylene oxide, propylene oxide), functionalized chemical auxiliaries (i.e., epoxidized vegetable oils), as well as high added-value fine chemicals (i.e., epoxidized terpenes). Several oxidants can be used for epoxidation (air, O2, hydrogen peroxide, organic hydroperoxides, peroxyacids) and the choice is linked to the substrate type, the features of the used catalyst, safety, economy, and sustainability of the overall process. The aim of this Special Issue on epoxidation reactions is to provide the reader with trans-disciplinary up-to-date information on different epoxidation systems, paying particular attention to the catalytic aspects of this transformation. 

Prof. Martino Di Serio
Dr. Matteo Guidotti
Guest Editors

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Keywords

  • Homogeneous
  • Heterogeneous
  • Enzymatic epoxidation
  • Hydroperoxides
  • Peroxyacids
  • Hydrogen peroxide

Published Papers (3 papers)

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Research

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14 pages, 2892 KiB  
Article
Epoxidation of Karanja (Millettia pinnata) Oil Methyl Esters in the Presence of Hydrogen Peroxide over a Simple Niobium-Containing Catalyst
by Nicola Scotti, Nicoletta Ravasio, Claudio Evangelisti, Rinaldo Psaro, Michele Penso, Prashant S. Niphadkar, Vijay V. Bokade and Matteo Guidotti
Catalysts 2019, 9(4), 344; https://doi.org/10.3390/catal9040344 - 08 Apr 2019
Cited by 14 | Viewed by 3100
Abstract
The synthesis, characterization and catalytic performance of a conceptually simple, novel NbOx-SiO2 catalyst are here described. The niobium(V)-silica catalyst was prepared starting from cheap and viable reactants, by alkaline deposition of NH4Nb(C2O4)2·H [...] Read more.
The synthesis, characterization and catalytic performance of a conceptually simple, novel NbOx-SiO2 catalyst are here described. The niobium(V)-silica catalyst was prepared starting from cheap and viable reactants, by alkaline deposition of NH4Nb(C2O4)2·H2O in the presence of fructose as a stabilizer and subsequent calcination. The NbOx-SiO2 solid (0.95 Nb wt.%) was tested in the liquid-phase epoxidation with aqueous hydrogen peroxide of methyl oleate, as a model substrate. It was then tested in the epoxidation of a mixture of methyl esters (FAMEs) obtained by transesterification with methanol and purification of karanja oil, extracted from the autochthonous Indian variety of Millettia pinnata tree. The catalyst showed a promising performance in terms of methyl oleate conversion (up to 75%) and selectivity to epoxide (up to 82%). It was then tested on the FAME mixture from karanja oil, where interesting conversion values were attained (up to 70%), although with lower selectivities and yields to the mixture of desired epoxidized FAMEs. The solid withstood four catalytic cycles overall, during which a non-negligible surface reorganization of the Nb(V) sites was observed. However, this restructuring did not negatively affect the performance of the catalysts in terms of conversion or selectivity. Full article
(This article belongs to the Special Issue Epoxidation Catalysis)
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14 pages, 4708 KiB  
Article
Cyclohexene Oxidation with H2O2 over Metal-Organic Framework MIL-125(Ti): The Effect of Protons on Reactivity
by Nataliya Maksimchuk, Ji Sun Lee, Artem Ayupov, Jong-San Chang and Oxana Kholdeeva
Catalysts 2019, 9(4), 324; https://doi.org/10.3390/catal9040324 - 02 Apr 2019
Cited by 13 | Viewed by 5330
Abstract
The catalytic performance of the titanium-based metal–organic framework MIL-125 was evaluated in the selective oxidation of cyclohexene (CyH) with environmentally friendly oxidants, H2O2 and tBuOOH. The catalytic activity of MIL-125 as well as the oxidant utilization efficiency and selectivity [...] Read more.
The catalytic performance of the titanium-based metal–organic framework MIL-125 was evaluated in the selective oxidation of cyclohexene (CyH) with environmentally friendly oxidants, H2O2 and tBuOOH. The catalytic activity of MIL-125 as well as the oxidant utilization efficiency and selectivity toward epoxide and epoxide-derived products can be greatly improved by acid additives (HClO4 or CF3SO3H). In the presence of 1 molar equivalent (relative to Ti) of a proton source, the total selectivity toward CyH epoxide and trans-cyclohexane-1,2-diol reached 75–80% at 38–43% alkene conversion after 45 min of reaction with 1 equivalent of 30% H2O2 at 50 °C. With 50% H2O2 as the oxidant, the total selectivity toward heterolytic oxidation products increased up to 92% at the same level of alkene conversion. N2 adsorption, powder X-ray diffraction (PXRD), and infrared (IR) spectroscopy studies before and after the catalytic oxidations confirmed the absence of structural changes in the Metal–organic framework (MOF) structure. MIL-125 was stable toward titanium leaching, behaved as a truly heterogeneous catalyst, and could easily be recovered and reused several times without any loss of the catalytic properties. Full article
(This article belongs to the Special Issue Epoxidation Catalysis)
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Review

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27 pages, 3942 KiB  
Review
Recent Progress in Application of Molybdenum-Based Catalysts for Epoxidation of Alkenes
by Yirui Shen, Pingping Jiang, Phyu Thin Wai, Qian Gu and Weijie Zhang
Catalysts 2019, 9(1), 31; https://doi.org/10.3390/catal9010031 - 02 Jan 2019
Cited by 77 | Viewed by 7600
Abstract
Epoxides are important industrial intermediates applied in a variety of industrial processes. During the production of epoxides, catalysts have played an irreplaceable and unique role. In this review, the historic progress of molybdenum-based catalysts in alkene epoxidation are covered and an outlook on [...] Read more.
Epoxides are important industrial intermediates applied in a variety of industrial processes. During the production of epoxides, catalysts have played an irreplaceable and unique role. In this review, the historic progress of molybdenum-based catalysts in alkene epoxidation are covered and an outlook on future challenge discussed. Efficient catalysts are demonstrated including soluble molybdenum complexes, polyoxometalates catalysts, molybdenum-containing metal organic frameworks, silica supported molybdenum-based catalysts, polymer supported molybdenum-based catalysts, magnetic molybdenum-based catalysts, hierarchical molybdenum-based catalysts, graphene-based molybdenum containing catalysts, photocatalyzed epoxidation catalysts, and some other systems. The effects of different solvents and oxidants are discussed and the mechanisms of epoxidation are summarized. The challenges and perspectives to further enhance the catalytic performances in alkenes epoxidation are presented. Full article
(This article belongs to the Special Issue Epoxidation Catalysis)
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