Traditional and Innovative Catalysts for Reactions of Industrial Interest

A special issue of Reactions (ISSN 2624-781X).

Deadline for manuscript submissions: closed (25 January 2024) | Viewed by 15147

Special Issue Editors


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Guest Editor
Department of Molecular Sciences and Nano Systems, Università Ca’ Foscari Venezia, Via Torino 155, 30172 Mestre Venezia, Italy
Interests: nanostructured materials; heterogeneous catalysts; sustainable processes; mesoporous materials; green applications
Special Issues, Collections and Topics in MDPI journals

E-Mail Website1 Website2
Guest Editor
Department of Molecular Sciences and Nano Systems, Università Ca’ Foscari Venezia, Via Torino 155, 30172 Mestre Venezia, Italy
Interests: heterogeneous catalysis; metal nanoparticles; oxidation reactions; industrial processes; biomass valorization
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Catalysis, which represents probably the oldest application of nanotechnology, is a key technology for the chemical industries of the future. We believe that through catalysis, it is possible to engineer a greener world. This Special Issue aims to provide a comprehensive overview of recent developments in the field of catalysts for the reaction of industrial interest. Heterogeneous, homogeneous, and enzymatic catalysis can be considered. Furthermore, different aspects—such as synthetic methodologies, characterization techniques, and process applications—can be addressed, together with the forthcoming megatrends and potential challenges.

All researchers working in the field are cordially invited to contribute original research papers or reviews to this Special Issue of Reactions. We look forward to receiving your submissions.

Prof. Dr. Michela Signoretto
Prof. Dr. Federica Menegazzo
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. Reactions is an international peer-reviewed open access quarterly 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

  • heterogeneous catalysts
  • homogeneous catalysts
  • enzymatic catalysts
  • industrial processes
  • nanoparticles
  • catalyst characterization
  • catalyst design

Published Papers (9 papers)

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Research

Jump to: Review

12 pages, 1496 KiB  
Article
A New Pd-Based Catalytic System for the Reductive Carbonylation of Nitrobenzene to Form N-(4-hydroxyphenyl)acetamide Selectively in One Pot
by Andrea Vavasori, Marco Capponi and Lucio Ronchin
Reactions 2023, 4(4), 725-736; https://doi.org/10.3390/reactions4040042 - 17 Nov 2023
Viewed by 1416
Abstract
N-(4-hydroxyphenyl)acetamide (commonly named paracetamol or acetaminophen) is a target molecules for many industries that produce chemicals for pharmaceutical applications. The industrial processes, however, use multistep procedures with low overall yield and/or severe drawbacks and problems in terms of sustainability. In the present paper, [...] Read more.
N-(4-hydroxyphenyl)acetamide (commonly named paracetamol or acetaminophen) is a target molecules for many industries that produce chemicals for pharmaceutical applications. The industrial processes, however, use multistep procedures with low overall yield and/or severe drawbacks and problems in terms of sustainability. In the present paper, a one-pot synthesis is proposed based on the reductive carbonylation of nitrobenzene catalyzed by Pd(II)-complexes. Usually, such a reaction leads to a mixture of different products, including aniline, 4-aminophenol and 1,3-diphenylurea. However, the selectivity towards the possible products strongly depends by the ligands on the Pd(II)-catalyst, but also by the nature of the solvent. According to this, we have found that when the reaction was carried out in dilute acetic acid as a solvent, the [PdCl2(dppb)] catalyst precursor leads in one pot to N-(4-hydroxyphenyl)acetamide. Under optimized reaction conditions, it was possible to produce N-(4-hydroxyphenyl)acetamide with a 85 mol % of selectivity in ca. 5 h. Full article
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17 pages, 5315 KiB  
Article
Multicomponent Reactions Promoted by Ecocatalyst from Metal Hyperaccumulating Plant Pluchea sagittalis
by Leonardo H. R. Alponti, Monize Picinini, Ernesto A. Urquieta-Gonzalez, Caroline S. da Silva, Simone Y. S. Silva, Sebastião C. Silva, Marilene N. de Oliveira, Juliana Viera, Maria Fatima das G. F. da Silva and Arlene G. Corrêa
Reactions 2023, 4(4), 552-568; https://doi.org/10.3390/reactions4040033 - 07 Oct 2023
Viewed by 1005
Abstract
Phytoremediation has been considered a sustainable environmental technology for heavy metals decontamination. In this work, we evaluated the metal contents by inductively coupled plasma optical emission spectrometry (ICP-OES) of three plant species collected in a mine in the Brazilian Amazonia area. Based on [...] Read more.
Phytoremediation has been considered a sustainable environmental technology for heavy metals decontamination. In this work, we evaluated the metal contents by inductively coupled plasma optical emission spectrometry (ICP-OES) of three plant species collected in a mine in the Brazilian Amazonia area. Based on this analysis, Pluchea sagitallis leaves were selected to prepare metallic ecocatalysts. The leaf ashes and the obtained ecocatalysts were characterized by ICP-OES, X-ray diffraction (XRD), scanning electron microscopy (SEM) and N2-physisorption measurements. Moreover, they were evaluated in the Biginelli and Hantzsch multicomponent reactions, furnishing the corresponding 3,4-dihydropyrimidin-2-(1H)-ones and 1,4-dihydropyridines with good to excellent yields. The best ecocatalyst was easily recovered and recycled in up to six reactions without a significant decrease in its performance. Full article
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13 pages, 1945 KiB  
Article
Comparative Analysis of Bio- and Chemo-Catalysts for the Synthesis of Flavour Compound Hexanal from Linoleic Acid
by Jan Drönner, Valentin Gala Marti, Simone Bandte, Anna Coenen, Ulrich Schörken and Matthias Eisenacher
Reactions 2023, 4(3), 518-530; https://doi.org/10.3390/reactions4030031 - 18 Sep 2023
Viewed by 854
Abstract
Hexanal, hexenal, nonenal and their corresponding alcohols are used as green notes in the fragrance and flavour industry. The production of bio-based hexanal starts from linoleic acid, which can be obtained from sunflower or safflower oil. The biocatalytic process utilizes C13-specific [...] Read more.
Hexanal, hexenal, nonenal and their corresponding alcohols are used as green notes in the fragrance and flavour industry. The production of bio-based hexanal starts from linoleic acid, which can be obtained from sunflower or safflower oil. The biocatalytic process utilizes C13-specific lipoxygenase (LOX) for hydroperoxidation and consecutive splitting with hydroperoxide lyase (HPL). In this study, we investigated the chemical splitting of the LOX product 13-HPODE in comparison to HPL catalysis. In addition, 13-HPODE was synthesized using enriched linoleic acid from safflower oil. Varying amounts of soybean flour suspension as a source of LOX yielded up to 60% HPODE with a regioselectivity of 92% towards 13-HPODE. Using low-toxicity Lewis acids like AlCl3 and ZrCl4, cleavage of the produced 13-HPODE was possible. A maximum hexanal yield of 22.9% was reached with AlCl3 under mild reaction conditions, though product degradation was an interfering process. Comparative trials with N-terminal truncated HPL from papaya revealed hexanal recovery within a comparable range. Additionally, we successfully demonstrated the viability of Hock rearrangement of 13-HPODE through heterogeneous catalysts. Notably, Beta zeolite and Montmorillonite K10 exhibited a turnover frequency (TOF) on par with common heterogeneous catalysts employed in industrial processes. Full article
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13 pages, 2312 KiB  
Article
Catalytic Valorisation of Biomass-Derived Levulinic Acid to Biofuel Additive γ-Valerolactone: Influence of Copper Loading on Silica Support
by Rajender Boddula, Paramasivam Shanmugam, Rajesh K. Srivatsava, Nabila Tabassum, Ramyakrishna Pothu, Ramachandra Naik, Aditya Saran, Balaga Viswanadham, Ahmed Bahgat Radwan and Noora Al-Qahtani
Reactions 2023, 4(3), 465-477; https://doi.org/10.3390/reactions4030028 - 05 Sep 2023
Cited by 3 | Viewed by 1405
Abstract
γ-valerolactone (GVL) is a crucial chemical feedstock used in the production of fuel additives, renewable fuels, and fine chemicals alternative to petroleum-based solvents and chemicals, supporting the transition to sustainable energy solutions. It is promptly acquired by hydrogenating levulinic acid (LA) in a [...] Read more.
γ-valerolactone (GVL) is a crucial chemical feedstock used in the production of fuel additives, renewable fuels, and fine chemicals alternative to petroleum-based solvents and chemicals, supporting the transition to sustainable energy solutions. It is promptly acquired by hydrogenating levulinic acid (LA) in a gaseous or liquid phase with a homogeneous or heterogeneous catalyst using a variety of recognized catalytic processes. Herein, this work focuses on the use of silica-supported copper (Cu/SiO2) catalysts for the gas-phase hydrogenation of LA to GVL under mild reaction conditions. The study analyzes how copper loading can affect the catalytic activity of the Cu/SiO2, while the flow rate of LA, time-on-stream, reaction temperature, and LA concentration affect the catalytic efficiency. The SiO2 support’s various Cu loadings are crucial for adjusting the catalytic hydrogenation activity. One of the studied catalysts, a 5 wt% Cu/SiO2 catalyst, demonstrated ~81% GVL selectivity with ~78% LA conversion and demonstrated stability for ~8 h while operating at atmospheric pressure and temperature (265 °C) and 0.5 mL/h of LA flow rate. The ability to activate hydrogen, high amount of acidic sites, and surface area were all discovered to be advantageous for increased GVL selectivity. Full article
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14 pages, 3693 KiB  
Article
Study of the Synthetic Approach Influence in Ni/CeO2-Based Catalysts for Methane Dry Reforming
by Marco Pizzolato, Giulia Da Pian, Elena Ghedini, Alessandro Di Michele, Federica Menegazzo, Giuseppe Cruciani and Michela Signoretto
Reactions 2022, 3(4), 634-647; https://doi.org/10.3390/reactions3040043 - 16 Dec 2022
Cited by 1 | Viewed by 1295
Abstract
This study focuses on the synthetic approach influence in morphostructural features and catalytic performances for Ni/CeO2 catalysts. Incipient wetness impregnation, coprecipitation and nitrate combustion were studied as catalyst preparation approaches, and the materials were then tested at 700 °C for methane dry [...] Read more.
This study focuses on the synthetic approach influence in morphostructural features and catalytic performances for Ni/CeO2 catalysts. Incipient wetness impregnation, coprecipitation and nitrate combustion were studied as catalyst preparation approaches, and the materials were then tested at 700 °C for methane dry reforming (MDR). The morphostructural properties of the materials were deeply studied using several techniques, such as temperature programmed reduction (TPR), to investigate reducibility and support-metal interaction, N2 physisorption to evaluate the porosity and the surface area, scanning electron microscopy (SEM) and X-ray diffraction (XRD) to estimate Ni dispersion, and temperature programmed oxidation (TPO) to identify the type and amount of coke formed on catalysts’ surface after reaction. From the data obtained, coprecipitation turned out to be the most suitable technique for this application because this catalyst was able to reach 70% of CO2 conversion and 30% methane conversion, with an H2 yield of 15% and 30% yield of CO at the end of the 30 h test. Moreover, it was also the catalyst with the highest metal dispersion, the strongest interaction with the support, and the lowest coke deposition. Full article
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12 pages, 7432 KiB  
Article
C-N, C-O and C-S Ullmann-Type Coupling Reactions of Arenediazonium o-Benzenedisulfonimides
by Achille Antenucci and Stefano Dughera
Reactions 2022, 3(2), 300-311; https://doi.org/10.3390/reactions3020022 - 02 Jun 2022
Cited by 5 | Viewed by 2998
Abstract
Arenediazonium o-benzenedisulfonimides have been used as efficient electrophilic partners in Cu(I) catalysed Ullmann-type coupling. The synthetic protocols are mild and easy, and produced either N-alkylanilines, aryl ethers, or thioethers in fairly good yields (18 positive examples, average yield 66%). o-Benzenedisulfonimide was [...] Read more.
Arenediazonium o-benzenedisulfonimides have been used as efficient electrophilic partners in Cu(I) catalysed Ullmann-type coupling. The synthetic protocols are mild and easy, and produced either N-alkylanilines, aryl ethers, or thioethers in fairly good yields (18 positive examples, average yield 66%). o-Benzenedisulfonimide was recovered at the end of the reactions and was reused to prepare the starting salts for further reactions. It is noteworthy that diazonium salts have been used as electrophilic partners in the Ullmann-type protocol for the first time. Full article
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11 pages, 1512 KiB  
Article
High Yielding, One-Pot Synthesis of Bis(1H-indazol-1-yl)methane Catalyzed by 3d-Metal Salts
by Natalie M. Lind, Natalie S. Joe, Brian S. Newell and Aimee M. Morris
Reactions 2022, 3(1), 59-69; https://doi.org/10.3390/reactions3010005 - 04 Jan 2022
Viewed by 2450
Abstract
Synthetic access to poly(indazolyl)methanes has limited their study despite their structural similarity to the highly investigated chelating poly(pyrazolyl)methanes and their potentially important indazole moiety. Herein is presented a high yielding, one-pot synthesis for the 3d-metal catalyzed formation of bis(1H-indazol-1-yl)methane [...] Read more.
Synthetic access to poly(indazolyl)methanes has limited their study despite their structural similarity to the highly investigated chelating poly(pyrazolyl)methanes and their potentially important indazole moiety. Herein is presented a high yielding, one-pot synthesis for the 3d-metal catalyzed formation of bis(1H-indazol-1-yl)methane from 1H-indazole utilizing dimethylsulfoxide as the methylene source. Complete characterization of bis(1H-indazol-1-yl)methane is given with 1H and 13C NMR, UV/Vis, FTIR, high resolution mass spectrometry and for the first time, single crystal X-ray diffraction. This simple, inexpensive pathway to yield exclusively bis(1H-indazol-1-yl)methane provides synthetic access to further investigate the coordination and potential applications of the family of bis(indazolyl)methanes. Full article
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Review

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13 pages, 1628 KiB  
Review
Chlorophyll Sensitization of TiO2: A Mini-Review
by Maria E. K. Fuziki, Angelo M. Tusset, Onélia A. A. dos Santos and Giane G. Lenzi
Reactions 2023, 4(4), 766-778; https://doi.org/10.3390/reactions4040044 - 01 Dec 2023
Viewed by 1208
Abstract
Recent studies have shown that chlorophyll sensitization can improve the performance of semiconductors like TiO2 in photocatalytic reactions and light-harvesting technologies, such as solar cells. Faced with the search for renewable energy sources and sustainable technologies, the application of this natural pigment [...] Read more.
Recent studies have shown that chlorophyll sensitization can improve the performance of semiconductors like TiO2 in photocatalytic reactions and light-harvesting technologies, such as solar cells. Faced with the search for renewable energy sources and sustainable technologies, the application of this natural pigment has been gaining prominence. The present work addresses some of the main possibilities of chlorophyll-TiO2 combination, presenting the most relevant aspects affecting chlorophyll extraction and TiO2 sensitization. Full article
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22 pages, 1984 KiB  
Review
Zeolite-Containing Co Catalysts for Fischer–Tropsch Synthesis with Tailor-Made Molecular-Weight Distribution of Hydrocarbons
by Lilia Sineva, Vladimir Mordkovich, Ekaterina Asalieva and Valeria Smirnova
Reactions 2023, 4(3), 359-380; https://doi.org/10.3390/reactions4030022 - 15 Jul 2023
Cited by 3 | Viewed by 1237
Abstract
The review is dedicated to the topical field of research aimed at creating catalysts combining several types of active sites. At the same time, the composition of Fischer–Tropsch synthesis (FTS) products can be controlled by changing the strength and concentration of the active [...] Read more.
The review is dedicated to the topical field of research aimed at creating catalysts combining several types of active sites. At the same time, the composition of Fischer–Tropsch synthesis (FTS) products can be controlled by changing the strength and concentration of the active sites and inter-site distances. A comparative analysis of the literature data allows to formulate the main principles of catalytic particles formation active in FTS and acid-catalyzed transformations of hydrocarbons: (1) the presence of weak Bronsted acid sites to control the cracking depth, (2) an availability of Bronsted acid sites for re-adsorption hydrocarbons and (3) weak Co-zeolite interaction to reduce methane formation. Full article
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