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Heterogeneous/Homogeneous Catalysis in Organic Synthesis – Recent Advances

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A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Catalysis in Organic and Polymer Chemistry".

Deadline for manuscript submissions: closed (10 June 2022) | Viewed by 23121

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Special Issue Editors

Dr. Agnieszka Siewniak

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Guest Editor

Silesian University of Technology, Faculty of Chemistry, Department of Chemical Organic Technology and Petrochemistry, 44-100 Gliwice, Poland
Interests: development of heterogeneous catalysis for fine chemicals synthesis; organocatalysis; phase transfer catalysis; reactions involving CO2; green chemistry

Prof. Dr. Anna Chrobok

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Guest Editor

Silesian University of Technology, Faculty of Chemistry, Department of Chemical Organic Technology and Petrochemistry, 44-100 Gliwice, Poland
Interests: heterogeneous and homogenous catalysis; designing of new methods of organic compounds synthesis; synthesis, characterization and application of ionic liquids; green chemistry

Special Issue Information

Dear Colleagues,

Catalysis is a fascinating phenomenon not only in natural processes but also in chemical ones. About 90% of the chemical industry technologies involve catalysts. The importance of catalysis also highlights the fact that one of the principles of green chemistry is devoted exclusively to this issue. Catalysis is a powerful tool in designing of sustainable, energy- and material-efficient and clean technologies

Important problems facing catalyst designers include understanding the factors affecting the activity of homogenous and heterogeneous catalysts, as well as developing catalysts with readily available active centers for reactants and stable under the process conditions.

Currently, the key challenge for the organic synthesis is the development of new catalysts that characterize both high activity and selectivity, and would ensure their easy separation from the reaction mixture. The removal of the catalyst after reaction is usually cost-intensive and energy-consuming. Therefore, two-way actions are being taken:

improvement of existing separation techniques and introduction of new, more energy-saving techniques
the use of heterogeneous catalysts. Such catalysts create the possibility of their effective recycling. Moreover, they can be used in flow reactors.

This Special Issue aims to collect both original research articles and reviews focusing, though not exclusively, on:

The application of heterogeneous and homogenous catalysis in organic synthesis;
Synthesis and characterization of new catalysts;
Designing of new methods of catalytic synthesis of organic compounds, meeting the requirements of sustainable development and principles of green chemistry.
Designing of immobilized catalyst on solid carriers such as polymers, carbon nanomaterials, silica, hybrid supports and others;

Dr. Agnieszka Siewniak
Prof. Dr. Anna Chrobok
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

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 2700 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

heterogeneous catalysis
heterogeneous catalysts
homogenous catalysis
homogenous catalyst
immobilized catalysts
supported catalysts
catalytic processes
design of catalysts
organic synthesis
fine chemicals synthesis
green chemistry

Published Papers (6 papers)

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Research

Jump to: Review

14 pages, 4028 KiB

Open AccessArticle

Catalytic Oxidation of Phosphine by Aqueous Copper–Ammonia Complexes

by Akbope K. Borangazieva, Yerzhan A. Boleubayev, Zhuldyz U. Ibraimova, Sholpan S. Itkulova and Gulshara S. Polimbetova

Catalysts 2023, 13(2), 271; https://0-doi-org.brum.beds.ac.uk/10.3390/catal13020271 - 25 Jan 2023

Viewed by 1427

Abstract

The furnace gas resulting from the electrothermal production of yellow phosphorus contains up to 95% CO, 2% O₂, 2% H₂, and 0.3–4.0% impurities, including phosphine (PH₃), yellow phosphorus (P₄), and hydrogen sulphide (H₂S), which are characterized by flammability, explosion hazardousness, corrosiveness, and high toxicity. The presence of toxic impurities does not allow the use of waste gases from phosphorus production, which are mainly composed of valuable carbon monoxide, as chemical raw materials and/or process fuel. The authors propose a method for the purification of furnace gas from the main toxic component, phosphine, by its oxidisation using aqueous copper–ammonia complexes as a catalyst. This approach allows the cleaning process to be conducted under mild conditions. The degree of purification of the model furnace gas from P components is 90–99%, depending on the process conditions. Full article

(This article belongs to the Special Issue Heterogeneous/Homogeneous Catalysis in Organic Synthesis – Recent Advances)

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13 pages, 3425 KiB

Open AccessArticle

Effect of Binding Modules Fused to Cutinase on the Enzymatic Synthesis of Polyesters

by Valerio Ferrario, Anamaria Todea, Lisa Wolansky, Nicola Piovesan, Alice Guarneri, Doris Ribitsch, Georg M. Guebitz, Lucia Gardossi and Alessandro Pellis

Catalysts 2022, 12(3), 303; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12030303 - 07 Mar 2022

Cited by 3 | Viewed by 2103

Abstract

In relation to the development of environmentally-friendly processing technologies for the continuously growing market of plastics, enzymes play an important role as green and sustainable biocatalysts. The present study reports the use of heterogeneous immobilized biocatalysts in solvent-free systems for the synthesis of aliphatic oligoesters with M_ws and monomer conversions up to 1500 Da and 74%, respectively. To improve the accessibility of hydrophilic and hydrophobic substrates to the surface of the biocatalyst and improve the reaction kinetic and the chain elongation, two different binding modules were fused on the surface of cutinase 1 from Thermobifida cellulosilytica. The fusion enzymes were successfully immobilized (>99% of bound protein) via covalent bonding onto epoxy-activated beads. To the best of our knowledge, this is the first example where fused enzymes are used to catalyze transesterification reactions for polymer synthesis purposes. Full article

(This article belongs to the Special Issue Heterogeneous/Homogeneous Catalysis in Organic Synthesis – Recent Advances)

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16 pages, 1936 KiB

Open AccessArticle

Chiral Quaternary Ammoniums Derived from Dehydroabietylamine: Synthesis and Application to Alkynylation of Isatin Derivatives Catalyzed by Silver

by Guanyu Jiang, Xinduo Sun, Fanrui Zhou, Kun Liang and Qian Chen

Catalysts 2021, 11(12), 1479; https://0-doi-org.brum.beds.ac.uk/10.3390/catal11121479 - 03 Dec 2021

Cited by 3 | Viewed by 2488

Abstract

Abietic acid and its derivatives have broadly been used in fine chemicals and are renewable resources. Its inherent chiral rigid tricyclic phenanthrene skeleton is unique. Its utilities in asymmetric catalysis remain to be explored. A series new amide-type chiral quaternary ammoniums bearing dehydroabietylamine were designed, and prepared by two convenient steps. Acylation of dehydroabietylamine with bromoacetyl chloride afforded amide holding bromoacetyl group in higher yields using triethyl amine as base. Subsequent quaternization reaction gave the desired amide-type chiral quaternary ammoniums. The new chiral quaternary ammoniums can be used as phase-transfer catalyst (PTC) for the transition metal-catalysed alkynylation of isatin derivatives. Full article

(This article belongs to the Special Issue Heterogeneous/Homogeneous Catalysis in Organic Synthesis – Recent Advances)

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17 pages, 8361 KiB

Open AccessArticle

Poly(imidazolium) Carbosilane Dendrimers: Synthesis, Catalytic Activity in Redox Esterification of α,β-Unsaturated Aldehydes and Recycling via Organic Solvent Nanofiltration

by Alena Krupková, Klára Kubátová, Lucie Červenková Šťastná, Petra Cuřínová, Monika Müllerová, Jindřich Karban, Jan Čermák and Tomáš Strašák

Catalysts 2021, 11(11), 1317; https://0-doi-org.brum.beds.ac.uk/10.3390/catal11111317 - 29 Oct 2021

Cited by 4 | Viewed by 1619

Abstract

Three series of poly(ionic) carbosilane dendrimers peripherally functionalized with imidazolium groups substituted on N-3 with methyl, isopropyl and 2,6-diisopropylphenyl (Dipp) were prepared up to the 3rd generation together with model monovalent imidazolium iodides and used as N-heterocyclic carbene (NHC) precursors. Catalytic activity of model and dendritic NHCs generated in situ by deprotonation with DBU was tested in redox esterification of α,β-unsaturated aldehydes and the influence of substitution, dendrimer generation, temperature and substrate structure on the reaction outcome was evaluated. Dipp substituted NHCs showed high activity and selectivity in the reaction with primary alcohols. Effectiveness of organic solvent nanofiltration for the recycling of dendritic NHCs was demonstrated on the 1st generation Dipp substituted catalyst in model redox esterification of cinnamaldehyde with benzyl alcohol. A marked increase in both activity and selectivity in the first four reaction runs was observed and this improved performance was preserved in the following catalytic cycles. Full article

(This article belongs to the Special Issue Heterogeneous/Homogeneous Catalysis in Organic Synthesis – Recent Advances)

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17 pages, 4177 KiB

Open AccessArticle

Structural Requirements for Chemoselective Ammonolysis of Ethylene Glycol to Ethanolamine over Supported Cobalt Catalysts

by Xianchi Lei, Guoding Gu, Yafei Hu, Haoshang Wang, Zhaoxia Zhang and Shuai Wang

Catalysts 2021, 11(6), 736; https://0-doi-org.brum.beds.ac.uk/10.3390/catal11060736 - 15 Jun 2021

Cited by 4 | Viewed by 5723

Abstract

Ethylene glycol is regarded as a promising C₂ platform molecule due to the fast development of its production from sustainable biomass. This study inquired the structural requirements of Co-based catalysts for the liquid-phase ammonolysis of ethylene glycol to value-added ethanolamine. We showed that the rate and selectivity of ethylene glycol ammonolysis on γ-Al₂O₃-supported Co catalysts were strongly affected by the metal particle size within the range of 2–10 nm, among which Co nanoparticles of ~4 nm exhibited both the highest ethanolamine selectivity and the highest ammonolysis rate based on the total Co content. Doping of a moderate amount of Ag further promoted the catalytic activity without affecting the selectivity. Combined kinetic and infrared spectroscopic assessments unveiled that the addition of Ag significantly destabilized the adsorbed NH₃ on the Co surface, which would otherwise be strongly bound to the active sites and inhibit the rate-determining dehydrogenation step of ethylene glycol. Full article

(This article belongs to the Special Issue Heterogeneous/Homogeneous Catalysis in Organic Synthesis – Recent Advances)

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Review

Jump to: Research

29 pages, 4836 KiB

Open AccessReview

Recent Advances in Homogeneous/Heterogeneous Catalytic Hydrogenation and Dehydrogenation for Potential Liquid Organic Hydrogen Carrier (LOHC) Systems

by Jun-Young Cho, Hahyeon Kim, Jeong-Eun Oh and Boyoung Y. Park

Catalysts 2021, 11(12), 1497; https://0-doi-org.brum.beds.ac.uk/10.3390/catal11121497 - 09 Dec 2021

Cited by 37 | Viewed by 7382

Abstract

Here, we review liquid organic hydrogen carriers (LOHCs) as a potential solution to the global warming problem due to the increased use of fossil fuels. Recently, hydrogen molecules have attracted attention as a sustainable energy carrier from renewable energy-rich regions to energy-deficient regions. The LOHC system is one a particularly promising hydrogen storage system in the “hydrogen economy”, and efficient hydrogen mass production that generates only benign byproducts can be applied in the industry. Therefore, this article presents hydrogenation and dehydrogenation, using homogeneous or heterogeneous catalysts, for several types of LOHCs, including formic acid/formaldehyde/ammonia, homocyclic compounds, nitrogen- and oxygen-containing compounds. In addition, it introduces LOHC system reactor types. Full article

(This article belongs to the Special Issue Heterogeneous/Homogeneous Catalysis in Organic Synthesis – Recent Advances)

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