Activation of Dioxygen and Liquid Phase Oxidation Catalysis for Fine Chemistry

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

Deadline for manuscript submissions: closed (31 January 2018) | Viewed by 43054

Special Issue Editor

Unité de Catalyse et Chimie du Solide, Université de Lille, Lille, France
Interests: surfactants; microemulsions; formulation; fragrances; dispersed systems; pickering emulsions; antioxidants; catalysis
Special Issues, Collections and Topics in MDPI journals

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

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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 (7 papers)

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Research

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2954 KiB  
Article
Catalytic Performance of Co3O4 on Different Activated Carbon Supports in the Benzyl Alcohol Oxidation
by Misael Cordoba, Cristian Miranda, Cecilia Lederhos, Fernando Coloma-Pascual, Alba Ardila, Gustavo A. Fuentes, Yannick Pouilloux and Alfonso Ramírez
Catalysts 2017, 7(12), 384; https://doi.org/10.3390/catal7120384 - 12 Dec 2017
Cited by 28 | Viewed by 6022
Abstract
Co3O4 particles were supported on a series of activated carbons (G60, CNR, RX3, and RB3). Incipient wetness method was used to prepare these catalysts. The effect of the structural and surface properties of the carbonaceous supports during oxidation of benzyl [...] Read more.
Co3O4 particles were supported on a series of activated carbons (G60, CNR, RX3, and RB3). Incipient wetness method was used to prepare these catalysts. The effect of the structural and surface properties of the carbonaceous supports during oxidation of benzyl alcohol was evaluated. The synthetized catalysts were characterized via IR, TEM, TGA/MS, XRD, TPR, AAS, XPS, and N2 adsorption/desorption isotherm techniques. Co3O4/G60 and Co3O4/RX3 catalysts have high activity and selectivity on the oxidation reaction reaching conversions above 90% after 6 h, without the presence of promoters. Catalytic performances show that differences in chemistry of support surface play an important role in activity and suggest that the presence of different ratios of species of cobalt and oxygenated groups on surface in Co3O4/G60 and Co3O4/RX3 catalysts, offered a larger effect synergic between both active phase and support increasing their catalytic activity when compared to the other tested catalysts. Full article
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1985 KiB  
Article
Highly ordered Nanomaterial Functionalized Copper Schiff Base Framework: Synthesis, Characterization, and Hydrogen Peroxide Decomposition Performance
by Fatemeh Rajabi, María Pinilla-de Dios and Rafael Luque
Catalysts 2017, 7(7), 216; https://doi.org/10.3390/catal7070216 - 19 Jul 2017
Cited by 5 | Viewed by 5505
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 [...] Read more.
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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4166 KiB  
Article
Catalytic Performance of MgO-Supported Co Catalyst for the Liquid Phase Oxidation of Cyclohexane with Molecular Oxygen
by Mingzhou Wu, Yu Fu, Wangcheng Zhan, Yanglong Guo, Yun Guo, Yunsong Wang and Guanzhong Lu
Catalysts 2017, 7(5), 155; https://doi.org/10.3390/catal7050155 - 13 May 2017
Cited by 28 | Viewed by 7901
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 [...] Read more.
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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2585 KiB  
Article
Organocatalytic Enantioselective Epoxidation of Some Aryl-Substituted Vinylidenebisphosphonate Esters: On the Way to Chiral Anti-Osteoporosis Drugs
by Andrea Chiminazzo, Laura Sperni, Alessandro Scarso and Giorgio Strukul
Catalysts 2017, 7(3), 90; https://doi.org/10.3390/catal7030090 - 20 Mar 2017
Cited by 5 | Viewed by 4906
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 [...] Read more.
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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2112 KiB  
Article
One-Pot Synthesis of (+)-Nootkatone via Dark Singlet Oxygenation of Valencene: The Triple Role of the Amphiphilic Molybdate Catalyst
by Bing Hong, Raphaël Lebeuf, Stéphanie Delbaere, Paul L. Alsters and Véronique Nardello-Rataj
Catalysts 2016, 6(12), 184; https://doi.org/10.3390/catal6120184 - 26 Nov 2016
Cited by 10 | Viewed by 6566
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 [...] Read more.
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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21 pages, 2993 KiB  
Review
Dioxygen Activation by Laccases: Green Chemistry for Fine Chemical Synthesis
by Cynthia Romero-Guido, Antonino Baez and Eduardo Torres
Catalysts 2018, 8(6), 223; https://doi.org/10.3390/catal8060223 - 24 May 2018
Cited by 27 | Viewed by 5158
Abstract
Laccases are enzymes with attractive features for the synthesis of fine chemicals. The friendly reaction conditions of laccases and their high conversion and selectivity make them particularly suitable for green methods of synthesis. In addition, laccases are enzymes with broad substrate variability, ease [...] Read more.
Laccases are enzymes with attractive features for the synthesis of fine chemicals. The friendly reaction conditions of laccases and their high conversion and selectivity make them particularly suitable for green methods of synthesis. In addition, laccases are enzymes with broad substrate variability, ease of production, and no need of cofactors or aggressive oxidizing agents. Among molecules oxidized by laccases are polycyclic aromatic hydrocarbons, azo dyes, pesticides, phenols, and pharmaceuticals. This article reviews the laccase-mediated oxidation of fine chemicals for the production of biologically active compounds. The main aspects of the enzymatic oxidation are summarized; potentials and limitations are identified and proposals to develop more robust catalysts are analyzed. Full article
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1606 KiB  
Review
Oxidation Catalysis by Enzymes in Microemulsions
by Evgenia Mitsou, Aristotelis Xenakis and Maria Zoumpanioti
Catalysts 2017, 7(2), 52; https://doi.org/10.3390/catal7020052 - 08 Feb 2017
Cited by 21 | Viewed by 6374
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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