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Catalysis of the Future: Trends in Structures, Processes and Applications

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A special issue of International Journal of Molecular Sciences (ISSN 1422-0067). This special issue belongs to the section "Materials Science".

Deadline for manuscript submissions: closed (31 March 2022) | Viewed by 18915

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Special Issue Editors

Prof. Dr. Avelino Corma

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Guest Editor

Instituto de Tecnología Química, UPV-CSIC, Universidad Politécnica de Valencia, Avda. de los Naranjos s/n, 46022 Valencia, Spain
Interests: heterogeneous catalysis; solid acid and basic catalysis; metal and oxides; nanoparticles as catalysts; heterogeneous transition metal complexes; catalytic cascade reactions

Prof. Dr. Lichen Liu

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Guest Editor

Department of Chemistry, Tsinghua University, Beijing 100084, China
Interests: heterogeneous catalysis; solid acid and basic catalysis; metal and oxides; nanoparticles as catalysts; heterogeneous transition metal complexes; catalytic cascade reactions

Special Issue Information

Dear Colleagues,

Heterogeneous catalysis plays a key role in addressing the world’s most concerning challenges. In recent years, the catalysis community has witnessed a trend that the boundaries between conventional thermal catalysis, photocatalysis and electrocatalysis are becoming less and less clear, as reflected in the common characterization techniques and concepts in the recent literature.

In general, the paradigm of catalysis research can be divided into three themes: development of new catalysts, studying the reaction mechanism and reaction engineering for a target process. Synthesizing catalysts with new formulations or new structures can always stimulate the discovery of new phenomena/knowledge in catalysis research. From a fundamental point of view, identifying the structures of solid catalysts at molecular and atomic level is vital for understanding the working mechanism and rational design of catalytic materials for desired reactions. This trend is reflected in the style of recent catalysis publications, in which multiple advanced characterization techniques are usually combined to reveal the structures of the active sites at atomic and molecular levels. In terms of the practical applications, the innovations in materials synthesis and reaction engineering have shown great potential in addressing the global challenges, such as climate change and the transition of energy sources from fossil fuels to renewable systems.

In this Special Issue (Catalysis of the Future: Trends in Structures, Processes and Applications), we will collect the works that present insights into the nature of the active sites in solid catalysts and novel applications in energy and environment. Specifically, works related to precise control of the catalyst’s structure/morphology/composition, advanced characterization of solid catalysts by microscopy and spectroscopy tools, innovation/optimization in important catalytic processes by reaction engineering and use of renewable energy/resources for production of chemicals/materials are welcome for submission to the journal for publication in this Special Issue.

Prof. Dr. Avelino Corma
Prof. Dr. Lichen Liu
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. International Journal of Molecular Sciences is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. There is an Article Processing Charge (APC) for publication in this open access journal. For details about the APC please see here. 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

zeolites
nanoparticles
nanoclusters
isolate metal atoms
single-site catalysts
in situ characterizations
reaction engineering
CO₂ transformation
photocatalysis
electrocatalysis

Published Papers (10 papers)

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Research

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19 pages, 9139 KiB

Open AccessArticle

Mild and Efficient Heterogeneous Hydrogenation of Nitroarenes Facilitated by a Pyrolytically Activated Dinuclear Ni(II)-Ce(III) Diimine Complex

by Jessica Michalke, Kirill Faust, Thomas Bögl, Stephan Bartling, Nils Rockstroh and Christoph Topf

Int. J. Mol. Sci. 2022, 23(15), 8742; https://doi.org/10.3390/ijms23158742 - 5 Aug 2022

Cited by 1 | Viewed by 1872

Abstract

We communicate the assembly of a solid, Ce-promoted Ni-based composite that was applied as catalyst for the hydrogenation of nitroarenes to afford the corresponding organic amines. The catalytically active material described herein was obtained through pyrolysis of a SiO₂-pellet-supported bimetallic Ni-Ce complex that was readily synthesized prior to use from a MeO-functionalized salen congener, Ni(OAc)₂·4 H₂O, and Ce(NO₃)₃·6 H₂O. Rewardingly, the requisite ligand for the pertinent solution phase precursor was accessible upon straightforward and time-saving imine condensation of ortho-vanillin with 1,3-diamino-2,2′-dimethylpropane. The introduced catalytic protocol is operationally simple in that the whole reaction set-up is quickly put together on the bench without the need of cumbersome handling in a glovebox or related containment systems. Moreover, the advantageous geometry and compact-sized nature of the used pellets renders the catalyst separation and recycling exceptionally easy. Full article

(This article belongs to the Special Issue Catalysis of the Future: Trends in Structures, Processes and Applications)

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15 pages, 6361 KiB

Open AccessArticle

The Benefits of Using Saccharose for Photocatalytic Water Disinfection

by Paulina Rokicka-Konieczna, Agata Markowska-Szczupak, Ewelina Kusiak-Nejman and Antoni W. Morawski

Int. J. Mol. Sci. 2022, 23(9), 4719; https://doi.org/10.3390/ijms23094719 - 25 Apr 2022

Cited by 2 | Viewed by 1254

Abstract

In this work, the characteristics of saccharose (sucrose)-modified TiO₂ (C/TiO₂) photocatalysts obtained using a hydrothermal method at low temperature (100 °C) are presented. The influence of C/TiO₂ on survivability and enzyme activity (catalase and superoxide dismutase) of Gram-negative bacteria Escherichia coli (ATCC 29425) and Gram-positive bacteria Staphylococcus epidermidis (ATCC 49461) under UV-A and artificial solar light (ASL) were examined. The obtained TiO₂-1%-S-100 photocatalysts were capable of total E. coli and S. epidermidis inactivation under ASL irradiation in less than 1 h. In addition, the impacts of sugars on the photocatalytic activity and disinfection performance are discussed. Full article

(This article belongs to the Special Issue Catalysis of the Future: Trends in Structures, Processes and Applications)

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21 pages, 2240 KiB

Open AccessArticle

Microwave-Assisted Base-Free Oxidation of Glucose with H₂O₂ on Gold- and Manganese-Containing SBA-15—Insight into Factors Affecting the Reaction Pathway

by Izabela Sobczak, Tsering Chödon Kowalska, Magdalena Nowicka and Maria Ziolek

Int. J. Mol. Sci. 2022, 23(9), 4639; https://doi.org/10.3390/ijms23094639 - 22 Apr 2022

Cited by 3 | Viewed by 1569

Abstract

The aim of this work was to gain insights into the role of manganese in MnSBA-15 support for gold in the base-free glucose oxidation with H₂O₂ using a microwave reactor. MnSBA-15 (manganese—acidity source) and SBA-15 (for comparison) were modified with Au (2.2 wt. %) and Cu (for comparison). The physicochemical properties of the catalysts were investigated by XRD, N₂ ads/des, TEM, UV-vis, XPS, pyridine adsorption combined with FTIR, ATR-FTIR, and 2-propanol decomposition. The effects of the Mn presence in the support, Au NPs size that determines the number of active Au centers, and the Fermi energy (E_F), together with the effects of the pore size, reaction temperature, and time on the activity and selectivity of the applied catalysts were assessed and discussed. It has been demonstrated that the presence of Mn generated Lewis acid centers which did not participate in glucose and H₂O₂ adsorption, and thus, were not directly involved in the reaction pathway. Both reagents were adsorbed on gold nanoparticles. H₂O₂ was decomposed to molecular oxygen which oxidized glucose to gluconic acid (50–90% of glucose conversion depending on the reaction time and ~100% selectivity). The presence of manganese in MnSBA-15 was responsible for increased Au NPs size and only slightly influenced the negative charge on gold particles. To achieve effective activity a compromise between the number of active gold species and the level of E_F has to be reached (for 5.7 nm Au NPs). Full article

(This article belongs to the Special Issue Catalysis of the Future: Trends in Structures, Processes and Applications)

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13 pages, 1977 KiB

Open AccessArticle

NMR Characterization of Long-Chain Fatty Acylcarnitine Binding to the Mitochondrial Carnitine/Acylcarnitine Carrier

by Ningning Zhang, Xiaopu Jia, Shuai Fan, Bin Wu, Shuqing Wang and Bo OuYang

Int. J. Mol. Sci. 2022, 23(9), 4608; https://doi.org/10.3390/ijms23094608 - 21 Apr 2022

Viewed by 1547

Abstract

The mitochondrial carnitine/acylcarnitine carrier (CAC) transports short-, medium- and long-carbon chain acylcarnitines across the mitochondrial inner membrane in exchange for carnitine. How CAC recognizes the substrates with various fatty acyl groups, especially long-chain fatty acyl groups, remains unclear. Here, using nuclear magnetic resonance (NMR) technology, we have shown that the CAC protein reconstituted into a micelle system exhibits a typical six transmembrane structure of the mitochondrial carrier family. The chemical shift perturbation patterns of different fatty acylcarnitines suggested that the segment A76–G81 in CAC specifically responds to the long-chain fatty acylcarnitine. Molecular dynamics (MD) simulations of palmitoyl-L-carnitine inside the CAC channel showed the respective interaction and motion of the long-chain acylcarnitine in CAC at the cytosol-open state and matrix-open state. Our data provided a molecular-based understanding of CAC structure and transport mechanism. Full article

(This article belongs to the Special Issue Catalysis of the Future: Trends in Structures, Processes and Applications)

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16 pages, 15856 KiB

Open AccessArticle

Photocatalytic Degradation of 4,4′-Isopropylidenebis(2,6-dibromophenol) on Magnetite Catalysts vs. Ozonolysis Method: Process Efficiency and Toxicity Assessment of Disinfection By-Products

by Joanna Kisała, Anna Tomaszewska, Adriana Barylyak, Yaroslav Bobitski and Maciej Balawejder

Int. J. Mol. Sci. 2022, 23(7), 3438; https://doi.org/10.3390/ijms23073438 - 22 Mar 2022

Cited by 1 | Viewed by 1654

Abstract

Flame retardants have attracted growing environmental concern. Recently, an increasing number of studies have been conducted worldwide to investigate flame-retardant sources, environmental distribution, living organisms’ exposure, and toxicity. The presented studies include the degradation of 4,4′-isopropylidenebis(2,6-dibromophenol) (TBBPA) by ozonolysis and photocatalysis. In the photocatalytic process, nano- and micro-magnetite (n-Fe₃O₄ and μ-Fe₃O₄) are used as a catalyst. Monitoring of TBBPA decay in the photocatalysis and ozonolysis showed photocatalysis to be more effective. Significant removal of TBBPA was achieved within 10 min in photocatalysis (ca. 90%), while for ozonation, a comparable effect was observed within 70 min. To determine the best method of TBBPA degradation concentration on COD and TOC, the removals were examined. The highest oxidation state was obtained for photocatalysis on μ-Fe₃O₄, whereas for n-Fe₃O₄ and ozonolysis, the COD/TOC ratio was lower. Acute toxicity results show noticeable differences in the toxicity of TBBPA and its degradation products to Artemia franciscana and Thamnocephalus platyurus. The EC₅₀ values indicate that TBBPA degradation products were toxic to harmful, whereas the TBPPA and post-reaction mixtures were toxic to the invertebrate species tested. The best efficiency in the removal and degradation of TBBPA was in the photocatalysis process on μ-Fe₃O₄ (reaction system 1). The examined crustaceans can be used as a sensitive test for acute toxicity evaluation. Full article

(This article belongs to the Special Issue Catalysis of the Future: Trends in Structures, Processes and Applications)

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11 pages, 1733 KiB

Open AccessArticle

Effect of Phosphorus Precursor, Reduction Temperature, and Support on the Catalytic Properties of Nickel Phosphide Catalysts in Continuous-Flow Reductive Amination of Ethyl Levulinate

by Yazhou Wang, Alexey L. Nuzhdin, Ivan V. Shamanaev, Evgeny G. Kodenev, Evgeny Yu. Gerasimov, Marina V. Bukhtiyarova and Galina A. Bukhtiyarova

Int. J. Mol. Sci. 2022, 23(3), 1106; https://doi.org/10.3390/ijms23031106 - 20 Jan 2022

Cited by 15 | Viewed by 1893

Abstract

Levulinic acid and its esters (e.g., ethyl levulinate, EL) are platform chemicals derived from biomass feedstocks that can be converted to a variety of valuable compounds. Reductive amination of levulinates with primary amines and H₂ over heterogeneous catalysts is an attractive method for the synthesis of N-alkyl-5-methyl-2-pyrrolidones, which are an environmentally friendly alternative to the common solvent N-methyl-2-pyrrolidone (NMP). In the present work, the catalytic properties of the different nickel phosphide catalysts supported on SiO₂ and Al₂O₃ were studied in a reductive amination of EL with n-hexylamine to N-hexyl-5-methyl-2-pyrrolidone (HMP) in a flow reactor. The influence of the phosphorus precursor, reduction temperature, reactant ratio, and addition of acidic diluters on the catalyst performance was investigated. The Ni₂P/SiO₂ catalyst prepared using (NH₄)₂HPO₄ and reduced at 600 °C provides the highest HMP yield, which reaches 98%. Although the presence of acid sites and a sufficient hydrogenating ability are important factors determining the pyrrolidone yield, the selectivity also depends on the specific features of EL adsorption on active catalytic sites. Full article

(This article belongs to the Special Issue Catalysis of the Future: Trends in Structures, Processes and Applications)

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16 pages, 4066 KiB

Open AccessArticle

Ru@hyperbranched Polymer for Hydrogenation of Levulinic Acid to Gamma-Valerolactone: The Role of the Catalyst Support

by Svetlana A. Sorokina, Stepan P. Mikhailov, Nina V. Kuchkina, Alexey V. Bykov, Alexander L. Vasiliev, Mariam G. Ezernitskaya, Andrey L. Golovin, Linda Zh. Nikoshvili, Mikhail G. Sulman and Zinaida B. Shifrina

Int. J. Mol. Sci. 2022, 23(2), 799; https://doi.org/10.3390/ijms23020799 - 12 Jan 2022

Cited by 11 | Viewed by 1939

Abstract

Hydrogenation of levulinic acid (LA) obtained from cellulose biomass is a promising path for production of γ-valerolactone (GVL)—a component of biofuel. In this work, we developed Ru nanoparticle containing nanocomposites based on hyperbranched pyridylphenylene polymer, serving as multiligand and stabilizing matrix. The functionalization of the nanocomposite with sulfuric acid significantly enhances the activity of the catalyst in the selective hydrogenation of LA to GVL and allows the reaction to proceed under mild reaction conditions (100 °C, 2 MPa of H₂) in water and low catalyst loading (0.016 mol.%) with a quantitative yield of GVL and selectivity up to 100%. The catalysts were successfully reused four times without a significant loss of activity. A comprehensive physicochemical characterization of the catalysts allowed us to assess structure-property relationships and to uncover an important role of the polymeric support in the efficient GVL synthesis. Full article

(This article belongs to the Special Issue Catalysis of the Future: Trends in Structures, Processes and Applications)

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16 pages, 4827 KiB

Open AccessArticle

Vypal2: A Versatile Peptide Ligase for Precision Tailoring of Proteins

by Dingpeng Zhang, Zhen Wang, Side Hu, Julien Lescar, James P. Tam and Chuan-Fa Liu

Int. J. Mol. Sci. 2022, 23(1), 458; https://doi.org/10.3390/ijms23010458 - 31 Dec 2021

Cited by 21 | Viewed by 2359

Abstract

The last two decades have seen an increasing demand for new protein-modification methods from the biotech industry and biomedical research communities. Owing to their mild aqueous reaction conditions, enzymatic methods based on the use of peptide ligases are particularly desirable. In this regard, the recently discovered peptidyl Asx-specific ligases (PALs) have emerged as powerful biotechnological tools in recent years. However, as a new class of peptide ligases, their scope and application remain underexplored. Herein, we report the use of a new PAL, VyPAL2, for a diverse range of protein modifications. We successfully showed that VyPAL2 was an efficient biocatalyst for protein labelling, inter-protein ligation, and protein cyclization. The labelled or cyclized protein ligands remained functionally active in binding to their target receptors. We also demonstrated on-cell labelling of protein ligands pre-bound to cellular receptors and cell-surface engineering via modifying a covalently anchored peptide substrate pre-installed on cell-surface glycans. Together, these examples firmly establish Asx-specific ligases, such as VyPAL2, as the biocatalysts of the future for site-specific protein modification, with a myriad of applications in basic research and drug discovery. Full article

(This article belongs to the Special Issue Catalysis of the Future: Trends in Structures, Processes and Applications)

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13 pages, 4224 KiB

Open AccessArticle

Development of Nickel- and Magnetite-Promoted Carbonized Cellulose Bead-Supported Bimetallic Pd–Pt Catalysts for Hydrogenation of Chlorate Ions in Aqueous Solution

by Emőke Sikora, Dániel Koncz-Horváth, Gábor Muránszky, Ferenc Kristály, Béla Fiser, Béla Viskolcz and László Vanyorek

Int. J. Mol. Sci. 2021, 22(21), 11846; https://doi.org/10.3390/ijms222111846 - 31 Oct 2021

Cited by 5 | Viewed by 1602

Abstract

Cellulose grains were carbonized and applied as catalyst supports for nickel- and magnetite-promoted bimetallic palladium- and platinum-containing catalysts. The bimetallic spherical aggregates of Pd and Pt particles were created to enhance the synergistic effect among the precious metals during catalytic processes. As a first step, the cellulose bead-based supports were impregnated by nitrate salts of nickel and iron and carbonized at 973 K. After this step, the nickel was in an elemental state, while the iron was in a magnetite form in the corresponding supports. Then, Pd and Pt particles were deposited onto the supports and the catalyst surface; precious metal nanoparticles (10–20 nm) were clustered inside spherical aggregated particles 500–600 nm in size. The final bimetallic catalysts (i.e., Pd–Pt/CCB, Pd–Pt/Ni–CCB, and Pd–Pt/Fe₃O₄–CCB) were tested in hydrogenation of chlorate ions in the aqueous phase. For the nickel-promoted Pd–Pt catalyst, a >99% chlorate conversion was reached after 45 min at 80 °C. In contrast, the magnetite-promoted sample reached an 84.6% chlorate conversion after 3 h. Reuse tests were also carried out with the catalysts, and in the case of Pd–Pt/Ni–CCB after five cycles, the catalytic activity only decreased by ~7% which proves the stability of the system. Full article

(This article belongs to the Special Issue Catalysis of the Future: Trends in Structures, Processes and Applications)

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Review

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39 pages, 6036 KiB

Open AccessReview

High-Throughput Strategies for the Design, Discovery, and Analysis of Bismuth-Based Photocatalysts

by Surya V. Prabhakar Vattikuti, Jie Zeng, Rajavaram Ramaraghavulu, Jaesool Shim, Alain Mauger and Christian M. Julien

Int. J. Mol. Sci. 2023, 24(1), 663; https://doi.org/10.3390/ijms24010663 - 30 Dec 2022

Cited by 3 | Viewed by 2183

Abstract

Bismuth-based nanostructures (BBNs) have attracted extensive research attention due to their tremendous development in the fields of photocatalysis and electro-catalysis. BBNs are considered potential photocatalysts because of their easily tuned electronic properties by changing their chemical composition, surface morphology, crystal structure, and band energies. However, their photocatalytic performance is not satisfactory yet, which limits their use in practical applications. To date, the charge carrier behavior of surface-engineered bismuth-based nanostructured photocatalysts has been under study to harness abundant solar energy for pollutant degradation and water splitting. Therefore, in this review, photocatalytic concepts and surface engineering for improving charge transport and the separation of available photocatalysts are first introduced. Afterward, the different strategies mainly implemented for the improvement of the photocatalytic activity are considered, including different synthetic approaches, the engineering of nanostructures, the influence of phase structure, and the active species produced from heterojunctions. Photocatalytic enhancement via the surface plasmon resonance effect is also examined and the photocatalytic performance of the bismuth-based photocatalytic mechanism is elucidated and discussed in detail, considering the different semiconductor junctions. Based on recent reports, current challenges and future directions for designing and developing bismuth-based nanostructured photocatalysts for enhanced photoactivity and stability are summarized. Full article

(This article belongs to the Special Issue Catalysis of the Future: Trends in Structures, Processes and Applications)

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