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Transition-Metal-Containing Bifunctional Catalysts: Design and Catalytic Applications

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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 (31 March 2023) | Viewed by 16504

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Dr. Linda Zh Nikoshvili

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Department of Biotechnology and Chemistry, Tver State Technical University, 22 A. Nikitina St., 170026 Tver, Russia
Interests: heterogeneous catalysis; selective hydrogenation; cross-coupling; polymer catalysts; cascade reactions; nanoparticulate catalysts

Prof. Dr. Lioubov Kiwi-Minsker

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Ecole Polytechnique Fédérale de Lausanne, GGRC-ISIC-EPFL, CH-1015 Lausanne, Switzerland
Interests: heterogeneous catalysis; selective hydrogenation; reaction kinetics; reaction engineering

Dr. Valentin Yu Doluda

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Guest Editor

Department of Biotechnology, Chemistry and Standardization, Tver State Technical University, Tver, Russia
Interests: catalysis; chemical technology; reactor design; microreactor technology; process simulation

Special Issue Information

Dear Colleagues,

We are pleased to invite you to a Special Issue dedicated to transition-metal-containing bifunctional catalysts, their design, and catalytic applications. Transition-metal-catalyzed reactions are highly demanded in modern chemical industry. Nanosized mono- and bimetallic particles as well as complexes of transition metals are well known as catalysts for many processes, such as hydrogenation, oxidation, deoxygenation, carbonylation, cross-coupling, etc. The search for novel supports, including polymeric ones, is of high importance, and the optimization of catalysts’ morphology and functionalities is a constantly developing field. This Special Issue is focused on bifunctional catalysts, which is an emerging field of catalysis including a variety of systems: bimetallic, magnetically separable, inorganic, and polymer ones. Polymers, while acting as macroligands, offer wide opportunities for stabilization of active phase and modification of catalytic properties of the resulting systems.

We welcome in this Special Issue both experimental and theoretical works related to transition-metal-containing bifunctional catalysts for different applications. The topics of this Special Issue include but are not limited to the following:

Homogeneous transition-metal-containing bifunctional catalysts;
Heterogeneous (such as inorganic and polymer-based) transition-metal-containing bifunctional catalysts;
Magnetically separable transition-metal-containing catalysts;
Bimetallic metal-containing polymer catalysts;
Kinetic study of transition-metal-catalyzed processes;
Computational research on transition-metal-containing catalysts.

Dr. Linda Zh Nikoshvili
Prof. Dr. Lioubov Kiwi-Minsker
Dr. Valentin Yu Doluda
Guest Editors

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Keywords

transition metal nanoparticles
polymer supports
inorganic supports
heterogeneous catalysis
homogeneous catalysis
bifunctional catalysis
DFT calculations

Published Papers (11 papers)

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Research

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20 pages, 8117 KiB

Open AccessArticle

Doped Ruthenium/Hypercrosslinked Polystyrene (HPS) Catalysts in the Modification of Fatty Acid Methyl Esters

by Romulo C. Dutra, Thatiane V. S. Martins, Delma da G. Rocha, Mario R. Meneghetti, Simoni M. P. Meneghetti, Mikhail G. Sulman, Valentina G. Matveeva and Paulo A. Z. Suarez

Catalysts 2023, 13(3), 630; https://doi.org/10.3390/catal13030630 - 21 Mar 2023

Cited by 1 | Viewed by 1339

Abstract

The modification of fatty substrates using heterogeneous catalysts have extensive industrial application and has an emphatic position in a sustainable context. Herein ruthenium, nickel, cobalt and copper-doped ruthenium, supported on hypercrosslinked polystyrene (HPS) catalysts were prepared by wet impregnation, characterized and applied on the modification of canola fatty acid methyl esters (FAME). The characterization showed a dispersive effect of doping metals over the ruthenium particles, the presence of acid sites and overall surface morphology, which allows targeting potential applications. The chosen modifications consisted of hydrogenation, hydroformylation, oxidative cleavage and deoxygenation, resulting in superb catalytic activities of over 99% conversions for hydrogenation and deoxygenation. The simplicity of the canola FAME composition allows the understanding of the catalytic processes and allows the upscale of more complex FAME matrixes. Finally, the obtained data stimulates further optimization studies for each application with a variation on the catalysts and the usage of residual fatty substrates, greatly enhancing the sustainability profile of the systems. Full article

(This article belongs to the Special Issue Transition-Metal-Containing Bifunctional Catalysts: Design and Catalytic Applications)

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19 pages, 19742 KiB

Open AccessFeature PaperArticle

Hydrogen Production by N-Heterocycle Dehydrogenation over Pd Supported on Aerogel-Prepared Mg-Al Oxides

by Danil M. Shivtsov, Anton P. Koskin, Sergey A. Stepanenko, Ekaterina V. Ilyina, Artem B. Ayupov, Alexander F. Bedilo and Vadim A. Yakovlev

Catalysts 2023, 13(2), 334; https://doi.org/10.3390/catal13020334 - 02 Feb 2023

Cited by 3 | Viewed by 1416

Abstract

Tetradecahydrophenazine (14HP) is a nitrogen-containing heterocycle compound with a high content of hydrogen that can be released during its dehydrogenation to phenazine (P). The high stability of the 14HP/P pair and relatively low dehydrogenation temperature make 14HP a promising organic hydrogen carrier. This manuscript is devoted to the investigation of hydrogen production by 14HP dehydrogenation over Pd supported on a series of magnesium-aluminum oxides prepared by the aerogel method. This technique made it possible to synthesize catalyst supports characterized by a high surface area and high concentration of surface active sites where active transition metals could be stabilized in a finely dispersed state. The synthesized aerogels had high specific surface areas and pore volumes. A surface area as high as 600 m²/g after calcination at 500 °C was observed for the mixed aerogel with an Mg:Al ratio of 1:4. An increase in the concentration of acidic electron-acceptor sites determined by EPR on the surface of the mixed magnesium-aluminum oxide supports with a high surface area prepared by the aerogel method was found to result in higher hydrogen production due to the faster dehydrogenation of sterically hindered nitrogen-containing tetradecahydrophenazine heterocycles. Full article

(This article belongs to the Special Issue Transition-Metal-Containing Bifunctional Catalysts: Design and Catalytic Applications)

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18 pages, 4192 KiB

Open AccessArticle

Influence of Synthesis Methodology on the Properties and Catalytic Performance of Tin, Niobium, and Tin-Niobium Oxides in Fructose Conversion

by Thatiane Veríssimo dos Santos Martins, Dhara Beatriz de Amorim Pryston, Simoni Margareti Plentz Meneghetti and Mario Roberto Meneghetti

Catalysts 2023, 13(2), 285; https://doi.org/10.3390/catal13020285 - 27 Jan 2023

Viewed by 1191

Abstract

Pure and mixed oxides were synthesized using three methods, namely, coprecipitation, hydrothermal treatment using CTAB and Pechini treatment using glycerol, and investigated for the transformation of fructose, aiming to determine the influence of textural, structural, and acid-base properties on conversion and selectivity. All systems led to fructose conversion in an aqueous medium, and the factors that influenced the transformation were the textural and structural properties, as well as the number of acid sites present in the catalysts. The best conversions were observed using mixed oxides, highlighting SnNb (CTAB) and SnNb (GLY), showing the importance of the modulation of properties using the synthesis method. All systems were selective mainly for 5-HMF (5-hydroxymethylfurfural) and, to a lesser extent, for the products of the retro-aldolic route, and this selectivity was preserved, regardless of the catalytic system used. Full article

(This article belongs to the Special Issue Transition-Metal-Containing Bifunctional Catalysts: Design and Catalytic Applications)

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15 pages, 13286 KiB

Open AccessArticle

Guaiacol to Aromatics: Efficient Transformation over In Situ-Generated Molybdenum and Tungsten Oxides

by Mariyam Mukhtarova, Maria Golubeva, Alexey Sadovnikov and Anton Maximov

Catalysts 2023, 13(2), 263; https://doi.org/10.3390/catal13020263 - 23 Jan 2023

Cited by 2 | Viewed by 1676

Abstract

The development of catalysts for the hydrodeoxygenation of bio-based feedstocks is an important step towards the production of fuels and chemicals from biomass. This paper describes in situ-generated bulk molybdenum and tungsten oxides in the hydrodeoxygenation of the lignin-derived compound guaiacol. The catalysts obtained were studied using powder X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, high-resolution transition electron microscopy, diffuse reflectance infrared Fourier transform spectroscopy, and Raman spectroscopy. The use of metal carbonyls as precursors was shown to promote the formation of amorphous molybdenum oxide and crystalline tungsten phosphide under hydrodeoxygenation conditions. The catalysts’ activity was investigated under various reaction conditions (temperature, H₂ pressure, solvent). MoO_x was more active in the partial and full hydrodeoxygenation of guaiacol at temperatures of 200–380 °C (5 MPa H₂, 6 h). However, cyclohexane, which is an undesirable product, was formed in significant amounts using MoO_x (5 MPa H₂, 6 h), while WO_x was more selective to aromatics. When using dodecane as a solvent (380 °C, 5 MPa H₂, 6 h), the benzene-toluene-xylenes fraction was obtained with a 96% yield over the WO_x catalyst. Full article

(This article belongs to the Special Issue Transition-Metal-Containing Bifunctional Catalysts: Design and Catalytic Applications)

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11 pages, 2228 KiB

Open AccessArticle

Investigation of CeO₂, MoO_3, and Ce₂(MoO₄)_3, Synthesized by the Pechini Method, as Catalysts for Fructose Conversion

by Dhara Beatriz de Amorim Pryston, Thatiane Veríssimo dos Santos Martins, Jailton Alves de Vasconcelos Júnior, Débora Olimpio da Silva Avelino, Mario Roberto Meneghetti and Simoni Margareti Plentz Meneghetti

Catalysts 2023, 13(1), 4; https://doi.org/10.3390/catal13010004 - 20 Dec 2022

Cited by 1 | Viewed by 1381

Abstract

Cerium oxide (Ce100), molybdenum oxide (Mo100), and a material containing Ce and Mo (CeMo) were synthesized by the Pechini method, using glycerol as a polyol. These materials were applied for fructose conversion in an aqueous medium. The characterization results show the formation of cerium molybdate (Ce₂(MoO₄)₃) for CeMo. Ce100 presented good thermal stability, and Mo100 sublimation of MoO₃ and polymolybdates was verified. CeMo exhibited a mass loss of 19%, associated with the sublimation of MoO₃ and polymolybdate species. Additionally, the existence of Bronsted and Lewis acid sites was confirmed, and the addition of Mo to Ce was an efficient strategy to increase the acidity. Regarding the catalytic activity (150 °C and 0.5 to 6 h), Ce100 exhibited low conversions and high selectivity to 5-hydroxymethylfurfural (5-HMF). For Mo100, high conversions, with a significant formation of insoluble materials, were detected. For CeMo, beyond the high activity, a lower formation of insoluble materials was noted. In this case, selectivity toward products from the retro–aldolic route and 5-HMF were obtained. These results indicate that the main factor influencing fructose conversion is an adequate combination of the acid sites. Recycling experiments were carried out, and stability was observed for four cycles, confirming the robustness of this system. Full article

(This article belongs to the Special Issue Transition-Metal-Containing Bifunctional Catalysts: Design and Catalytic Applications)

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18 pages, 3331 KiB

Open AccessArticle

Cr-Zn/Ni-Containing Nanocomposites as Effective Magnetically Recoverable Catalysts for CO₂ Hydrogenation to Methanol: The Role of Metal Doping and Polymer Co-Support

by Svetlana A. Sorokina, Nina V. Kuchkina, Maxim E. Grigoriev, Alexey V. Bykov, Andrey K. Ratnikov, Valentin Yu. Doluda, Mikhail G. Sulman and Zinaida B. Shifrina

Catalysts 2023, 13(1), 1; https://doi.org/10.3390/catal13010001 - 20 Dec 2022

Cited by 2 | Viewed by 1656

Abstract

CO₂ hydrogenation to methanol is an important process that could solve the problem of emitted CO₂ that contributes to environmental concern. Here we developed Cr-, Cr-Zn-, and Cr-Ni-containing nanocomposites based on a solid support (SiO₂ or Al₂O₃) with embedded magnetic nanoparticles (NPs) and covered by a cross-linked pyridylphenylene polymer layer. The decomposition of Cr, Zn, and Ni precursors in the presence of supports containing magnetic oxide led to formation of amorphous metal oxides evenly distributed over the support-polymer space, together with the partial diffusion of metal species into magnetic NPs. We demonstrated the catalytic activity of Cr₂O₃ in the hydrogenation reaction of CO₂ to methanol, which was further increased by 50% and 204% by incorporation of Ni and Zn species, respectively. The fine intermixing of metal species ensures an enhanced methanol productivity. Careful adjustment of constituent elements, e.g., catalytic metal, type of support, presence of magnetic NPs, and deposition of hydrophobic polymer layer contributes to the synergetic promotional effect required for activation of CO₂ molecules as well. The results of catalytic recycle experiments revealed excellent stability of the catalysts due to protective role of hydrophobic polymer. Full article

(This article belongs to the Special Issue Transition-Metal-Containing Bifunctional Catalysts: Design and Catalytic Applications)

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10 pages, 1733 KiB

Open AccessFeature PaperArticle

Transfer Hydrogenation of Biomass-Like Phenolic Compounds and 2-PrOH over Ni-Based Catalysts Prepared Using Supercritical Antisolvent Coprecipitation

by Alexey Philippov, Nikolay Nesterov and Oleg Martyanov

Catalysts 2022, 12(12), 1655; https://doi.org/10.3390/catal12121655 - 15 Dec 2022

Cited by 3 | Viewed by 1068

Abstract

Transfer hydrogenation (TH) is considered as one of the most promising ways to convert biomass into valuable products. This study aims to demonstrate the performance of high-loaded Ni-based catalysts in the TH of phenolic compounds such as guaiacol and dimethoxybenzenes. The experiments were carried out under supercritical conditions at 250 °C using 2-PrOH as the only hydrogen donor. Ni-SiO₂ and NiCu-SiO₂ were synthesized using the eco-friendly original method based on supercritical antisolvent coprecipitation. It has been found that guaiacol is rapidly converted into 2-methoxycyclohexanol and cyclohexanol, while the presence of Cu impedes the formation of the latter product. Transformations of dimethoxybenzene position isomers are slower and result in different products. Thus, 1,3-dimethoxybenzene loses oxygen atoms transform into methoxycyclohexane and cyclohexanol, whereas the saturation of the aromatic ring is more typical for other isomers. The Cu addition increases specific catalytic activity in the TH of 1,2-and 1,3-dimethoxybenzene compared to the Cu-free catalyst. Full article

(This article belongs to the Special Issue Transition-Metal-Containing Bifunctional Catalysts: Design and Catalytic Applications)

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9 pages, 1340 KiB

Open AccessArticle

Effect of Cr on a Ni-Catalyst Supported on Sibunite in Bicyclohexyl Dehydrogenation in Hydrogen Storage Application

by Leonid M. Kustov and Alexander N. Kalenchuk

Catalysts 2022, 12(12), 1506; https://doi.org/10.3390/catal12121506 - 24 Nov 2022

Cited by 3 | Viewed by 1194

Abstract

A comparison of the activity of mono- and bimetallic Ni-Cr/C catalysts deposited on a carbon carrier (sibunite) in the bicyclohexyl dehydrogenation reaction as a stage of hydrogen evolution in hydrogen storage systems is carried out. The interaction of Ni and Cr supported onto the carbon carrier—sibunite in bimetallic NiCr systems affects the change in the parameters of the crystal lattice of nickel, compared with the FCC lattice of Ni, as shown by the methods of XPS, TPR, XRD, high-resolution TEM and electron diffraction. Full article

(This article belongs to the Special Issue Transition-Metal-Containing Bifunctional Catalysts: Design and Catalytic Applications)

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22 pages, 7017 KiB

Open AccessArticle

Reductive Catalytic Fractionation of Spruce Wood over Ru/C Bifunctional Catalyst in the Medium of Ethanol and Molecular Hydrogen

by Oxana P. Taran, Angelina V. Miroshnikova, Sergey V. Baryshnikov, Aleksandr S. Kazachenko, Andrey M. Skripnikov, Valentin V. Sychev, Yuriy N. Malyar and Boris N. Kuznetsov

Catalysts 2022, 12(11), 1384; https://doi.org/10.3390/catal12111384 - 08 Nov 2022

Cited by 8 | Viewed by 1752

Abstract

Reductive catalytic fractionation (RCF) has emerged as an effective lignin-first biorefinery strategy to depolymerize lignin into tractable fragments in high yields. Herein, we propose the RCF of spruce wood over a Ru/C bifunctional catalyst in the medium of ethanol and molecular hydrogen to produce monomeric phenolic compounds from lignin, polyols from hemicelluloses, and microcrystalline cellulose. This contribution attempts to elucidate the role of the Ru/C bifunctional catalysts characteristics. The results clarify the particular effect of the carbon support acidity, catalyst grain size, content and dispersion of Ru on the effectiveness of lignin and hemicelluloses extraction and the yields of liquid and gaseous products. The most efficient catalysts for RCF of spruce wood, providing high yields of the monomeric phenols, glycols, and solid product with content of cellulose up to 90 wt%, bear 3 wt% of Ru with a dispersion of 0.94 based on an acidic oxidized graphite-like carbon support Sibunit^®, and having a grain size of 56–94 μm. The Ru/C catalysts intensify the reactions of hydrodeoxygenation of liquid products from lignin. The main phenolic monomers are 4-propyl guaiacol, 4-propenyl guaiacol, and 4-propanol guaiacol. We explored the effect of the process temperature and time on the yield and composition of the liquid, solid, and gaseous products of spruce wood RCF. The optimal trade-off between the yields of phenolic monomers (30.0 wt%). polyols (18.6 wt%) and the solid product containing 84.4 wt% of cellulose is reached at 225 °C and 3 h over the most acidic Ru/C catalyst. Full article

(This article belongs to the Special Issue Transition-Metal-Containing Bifunctional Catalysts: Design and Catalytic Applications)

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Review

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49 pages, 16582 KiB

Open AccessReview

Recent Progress in Pd-Catalyzed Tandem Processes

by Linda Z. Nikoshvili and Valentina G. Matveeva

Catalysts 2023, 13(8), 1213; https://doi.org/10.3390/catal13081213 - 15 Aug 2023

Cited by 2 | Viewed by 1214

Abstract

In recent years, Pd-containing catalytic systems for tandem processes have gained special attention due to their enhanced catalytic properties and their possibility of performing several reactions without the necessity of separating the intermediates. In this review, recent progress in Pd-catalyzed tandem processes is considered. Three types of catalytic systems are described: homogeneous catalysts (including immobilized Pd complexes); heterogeneous catalysts supported on oxides, MOFs, COFs, etc., with particular attention to the supports containing acid/base sites; and metal-enzyme catalysts for chemoenzymatic tandem processes applied in fine organic synthesis and biotechnology. For homogeneous Pd-catalyzed reactions, different tandem reactions were considered, i.e., cross-coupling, cyclization, carbonylation, isomerization, alkylation, arylation, etc. Full article

(This article belongs to the Special Issue Transition-Metal-Containing Bifunctional Catalysts: Design and Catalytic Applications)

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14 pages, 1668 KiB

Open AccessReview

Plant-Biomass-Derived Carbon Materials as Catalyst Support, A Brief Review

by Antonina A. Stepacheva, Mariia E. Markova, Yury V. Lugovoy, Yury Yu. Kosivtsov, Valentina G. Matveeva and Mikhail G. Sulman

Catalysts 2023, 13(4), 655; https://doi.org/10.3390/catal13040655 - 27 Mar 2023

Cited by 5 | Viewed by 1934

Abstract

Carbon materials are widely used in catalysis as effective catalyst supports. Carbon supports can be produced from coal, organic precursors, biomass, and polymer wastes. Biomass is one of the promising sources used to produce carbon-based materials with a high surface area and a hierarchical structure. In this review, we briefly discuss the methods of biomass-derived carbon supported catalyst preparation and their application in biodiesel production, organic synthesis reactions, and electrocatalysis. Full article

(This article belongs to the Special Issue Transition-Metal-Containing Bifunctional Catalysts: Design and Catalytic Applications)

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