Special Issue "Activation of Dioxygen and Liquid Phase Oxidation Catalysis for Fine Chemistry"

A special issue of Catalysts (ISSN 2073-4344).

Deadline for manuscript submissions: 31 January 2018

Special Issue Editor

Guest Editor
Prof. Dr. Véronique Nardello-Rataj

Unité de Catalyse et Chimie du Solide, Université Lille1, UMR CNRS 8181, 59655 Villeneuve d'Ascq, France
Website | E-Mail
Interests: singlet molecular oxygen; hydrogen peroxide; catalytic oxidation; non conventional reaction media; Pickering emulsions; polyphasic microemulsions; Pickering interfacial catalysis; balanced catalytic surfactants; amphiphilic catalytic nanoparticles; physicochemistry of nano- and microdispersed systems

Special Issue Information

Dear Colleagues,

Green chemistry has emerged as a very important topic for sustainable chemistry. Research is now guided by a set of principles that must be taken into account, e.g., (1) the design of processes that minimize the amount of by-products and wastes, (2) the use of safe and benign reactants and solvents, (3) the development of catalytic processes, etc. In this context, catalytic oxidation plays a central role, in particular in the fine-chemical industry. Many industrial processes still involve the use of stoichiometric reagents which have to be replaced by catalytic systems. Over the last few decades, several elegant liquid phase catalytic oxidation reactions involving oxygen or hydrogen peroxide as green oxidants have been explored. They include, for example, biphasic catalysis, dendrimers, hyperbranched polymers, ionic liquids, microemulsions and emulsions, organized systems, etc. using various efficient and selective tailor-made chemical and biochemical catalysts.

The aim of this Special Issue is to cover the promising recent research and novel trends in the field of catalytic oxidation with a special focus on liquid phase catalytic oxidation. Thus, new catalysts, new oxidants derived from oxygen activation, original reaction media, etc., used for the synthesis of chemicals for the fine chemistry will be of interest for this Special Issue, as well as new mechanistic insights into the oxidative processes.

Prof. Dr. Véronique Nardello-Rataj
Guest Editor

Manuscript Submission Information

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Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Catalysts is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 1000 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • catalytic oxidation

  • oxygen activation

  • hydrogen peroxide

  • mechanisms

  • non-conventional reaction media

  • enzymatic oxidation catalysis

  • fine chemistry

  • industrial prospects for oxidation and fine chemistry

Published Papers (5 papers)

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Research

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Open AccessArticle Highly ordered Nanomaterial Functionalized Copper Schiff Base Framework: Synthesis, Characterization, and Hydrogen Peroxide Decomposition Performance
Catalysts 2017, 7(7), 216; doi:10.3390/catal7070216
Received: 7 June 2017 / Revised: 11 July 2017 / Accepted: 12 July 2017 / Published: 19 July 2017
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Abstract
An immobilized copper Schiff base tridentate complex was prepared in three steps from SBA-15 supports. The immobilized copper nanocatalyst (heterogeneous catalyst) was characterized by Fourier transform infrared spectroscopy (FT-IR), cross polarization magic angle spinning (CP-MAS), 13-carbon nuclear magnetic resonance (13C-NMR), atomic
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An immobilized copper Schiff base tridentate complex was prepared in three steps from SBA-15 supports. The immobilized copper nanocatalyst (heterogeneous catalyst) was characterized by Fourier transform infrared spectroscopy (FT-IR), cross polarization magic angle spinning (CP-MAS), 13-carbon nuclear magnetic resonance (13C-NMR), atomic absorption spectroscopy (AAS), thermogravimetric analysis (TGA), and N2-physisorption. Moreover, morphological and structural features of the immobilized nanocatalyst were analyzed using transmission electron microscopy (TEM) and X-ray powder diffraction spectrometry (PXRD). After characterizing the nanocatalyst, the catalytic activity was determined in hydrogen peroxide (H2O2) decomposition. The high decomposition yield of H2O2 was obtained for low-loaded copper content materials at pH 7 and at room temperature. Furthermore, the nanocatalyst exhibited high activity and stability under the investigated conditions, and could be recovered and reused for at least five consecutive times without any significant loss in activity. No copper leaching was detected during the reaction by AAS measurements. Full article
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Open AccessArticle Catalytic Performance of MgO-Supported Co Catalyst for the Liquid Phase Oxidation of Cyclohexane with Molecular Oxygen
Catalysts 2017, 7(5), 155; doi:10.3390/catal7050155
Received: 21 March 2017 / Revised: 27 April 2017 / Accepted: 9 May 2017 / Published: 13 May 2017
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Abstract
A highly-efficient and stable MgO-supported Co (Co/MgO) catalyst was developed for the oxidation of cyclohexane with oxygen. The effects of the Co loading and support on the catalytic activity of the supported Co3O4 catalyst were investigated. The results show that
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A highly-efficient and stable MgO-supported Co (Co/MgO) catalyst was developed for the oxidation of cyclohexane with oxygen. The effects of the Co loading and support on the catalytic activity of the supported Co3O4 catalyst were investigated. The results show that the Co supported on MgO presented excellent activity and stability. When the Co/MgO catalyst with the Co content of 0.2 wt% (0.2%Co/MgO) was used, 12.5% cyclohexane conversion and 74.7% selectivity to cyclohexanone and cyclohexanol (KA oil) were achieved under the reaction conditions of 0.5 MPa O2 and 140 °C for 4 h. After being repeatedly used 10 times, its catalytic activity was hardly changed. Further research showed that the high catalytic performance of the 0.2%Co/MgO catalyst is attributed to its high oxygen-absorbing ability and the high ratio between the amount of weak and medium base sites with the help of the synergistic interaction between Co and MgO. Full article
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Open AccessArticle Organocatalytic Enantioselective Epoxidation of Some Aryl-Substituted Vinylidenebisphosphonate Esters: On the Way to Chiral Anti-Osteoporosis Drugs
Catalysts 2017, 7(3), 90; doi:10.3390/catal7030090
Received: 18 January 2017 / Revised: 7 March 2017 / Accepted: 13 March 2017 / Published: 20 March 2017
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Abstract
The synthesis of a new class of epoxide derivatives from prochiral vinylidene bisphosphonate (VBP) precursors is reported using hydrogen peroxide as the terminal oxidant. The reaction is carried out using a series of possible organic activators having a basic character, with the best
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The synthesis of a new class of epoxide derivatives from prochiral vinylidene bisphosphonate (VBP) precursors is reported using hydrogen peroxide as the terminal oxidant. The reaction is carried out using a series of possible organic activators having a basic character, with the best results being observed using quinine and sparteine. These activators not only provide from good to excellent epoxide yields with a large variety of VBPs, but also interesting enantioselectivities in the 67%–96% ee range, at least in the case of the Ph and m-MeO–Ph VBP derivatives, opening the way to a number of chiral anti-osteoporosis potentially active pharmaceutical ingredients. Full article
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Open AccessFeature PaperArticle One-Pot Synthesis of (+)-Nootkatone via Dark Singlet Oxygenation of Valencene: The Triple Role of the Amphiphilic Molybdate Catalyst
Catalysts 2016, 6(12), 184; doi:10.3390/catal6120184
Received: 16 September 2016 / Revised: 7 November 2016 / Accepted: 18 November 2016 / Published: 26 November 2016
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Abstract
Efficient one-pot catalytic synthesis of (+)-nootkatone was performed from (+)-valencene using only hydrogen peroxide and amphiphilic molybdate ions. The process required no solvent and proceeded in three cascade reactions: (i) singlet oxygenation of valencene according to the ene reaction; (ii) Schenck rearrangement of
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Efficient one-pot catalytic synthesis of (+)-nootkatone was performed from (+)-valencene using only hydrogen peroxide and amphiphilic molybdate ions. The process required no solvent and proceeded in three cascade reactions: (i) singlet oxygenation of valencene according to the ene reaction; (ii) Schenck rearrangement of one hydroperoxide into the secondary β-hydroperoxide; and (iii) dehydration of the hydroperoxide into the desired (+)-nootkatone. The solvent effect on the hydroperoxide rearrangement is herein discussed. The amphiphilic dimethyldioctyl ammonium molybdate, which is also a balanced surfactant, played a triple role in this process, as molybdate ions catalyzed at both Step 1 and Step 3 and it allowed the rapid formation of a three-phase microemulsion system that highly facilitates product recovery. Preparative synthesis of the high added value (+)-nootkatone was thus performed at room temperature with an isolated yield of 46.5%. This is also the first example of a conversion of allylic hydroperoxides into ketones catalyzed by molybdate ions. Full article
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Review

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Open AccessFeature PaperReview Oxidation Catalysis by Enzymes in Microemulsions
Catalysts 2017, 7(2), 52; doi:10.3390/catal7020052
Received: 12 January 2017 / Revised: 27 January 2017 / Accepted: 4 February 2017 / Published: 8 February 2017
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Abstract
Microemulsions are regarded as “the ultimate enzyme microreactors” for liquid oxidations. Their structure, composed of water nanodroplets dispersed in a non-polar medium, provides several benefits for their use as media for enzymatic transformations. They have the ability to overcome the solubility limitations of
[...] Read more.
Microemulsions are regarded as “the ultimate enzyme microreactors” for liquid oxidations. Their structure, composed of water nanodroplets dispersed in a non-polar medium, provides several benefits for their use as media for enzymatic transformations. They have the ability to overcome the solubility limitations of hydrophobic substrates, enhance the enzymatic activity (superactivity phenomenon) and stability, while providing an interface for surface-active enzymes. Of particular interest is the use of such systems to study biotransformations catalyzed by oxidative enzymes. Nanodispersed biocatalytic media are perfect hosts for liquid oxidation reactions catalyzed by many enzymes such as heme peroxidases, phenoloxidases, cholesterol oxidase, and dehydrogenases. The system’s composition and structural properties are important for better understanding of nanodispersion-biocatalyst interactions. Full article
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