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Nano-Porous Materials for Catalytic Systems in Green Chemistry Processes

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

Deadline for manuscript submissions: closed (30 June 2023) | Viewed by 29038

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Special Issue Editors

Prof. Dr. Roman Dziembaj

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Guest Editor

Jagiellonian University in Kraków, Faculty of Chemistry, Chemical Technology Department, (Emeritus), Gronostajowa 2, 30-387 Kraków, Poland
Interests: transition metal oxides as catalytic and energy storage materials; nano-structured catalysts—synthesis, activation, and deactivation; functionalization of carbon and inorganic porous materials; green chemistry processes; environmental catalysis

Prof. Dr. Lucjan Chmielarz

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Guest Editor

Faculty of Chemistry, Jagiellonian University in Kraków, Gronostajowa 2, 30-387 Kraków, Poland
Interests: heterogeneous catalysis for environmental applications; zeolites and their functionalization for catalysis and adsorption; clay minerals—intercalation and acid modifications; mesoporous silica materials for catalytic applications; layered double hydroxides and their calcined forms for environmental applications
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Nano-porous materials, especially those with ordered and well defined porous structures, have been known as catalytic supports and catalysts of various chemical reactions, including industrial chemical processes and pollution control technologies. Recent trends in studies of such nano-porous materials for catalysis are focused, among others, on the synthesis of catalysts with dual micro-mesoporous porosity, crystalline mesoporous aluminosilicates, as well as deposition of catalytically active components in uniform and stable forms. Progress in these studies has opened new perspectives for more effective catalytic systems with improved activity, selectivity, and stability. The design of new technologies as well as the retrofitting of existing technologies must fulfil requirements of green chemistry principles, such as limitation of waste production, use of reactants with no or limited environmental impact, processes with decreased energy consumption, use of renewable feedstock, and the preferential role of catalytic reagents over stoichiometric reagents. Meeting these requirements can be supported by application of advanced catalytic systems based on nano-porous materials implemented with nano-sized transition metal species. Thus, the main goal of this Special Issue is to present progress in the synthesis of advanced catalysts for green chemistry processes based on nano-porous materials.

Submissions to this Special Issue, “Nano-Porous Materials in Green Chemistry Processes”, are welcome in the form of original research papers or short reviews reflecting upon the knowledge in the field of nano-porous materials and their applications in green chemistry processes. These include, but are not limited to, zeolites, mesoporous silicas, modified clay minerals, nano-sized transition metals oxide species, active carbons, carbon nanotubes and their applications in green chemistry processes, environmental catalysis, eco-friendly synthesis of fuels and chemicals, and biomass valorization.

Prof. Dr. Roman Dziembaj
Prof. Dr. Lucjan Chmielarz
Guest Editors

Manuscript Submission Information

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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

Zeolites
Mesoporous silicas
Modified clay minerals
Nano-structured catalysts
Nano-sized transition metal oxide species
Functional carbon materials
Green chemistry processes
Environmental and sustainable catalysis
Eco-friendly synthesis of fuels and chemicals
Biomass valorization

Published Papers (11 papers)

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Research

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12 pages, 5302 KiB

Open AccessArticle

Three-Dimensional Hierarchical Hydrotalcite–Silica Sphere Composites as Catalysts for Baeyer–Villiger Oxidation Reactions Using Hydrogen Peroxide

by Daniel Cosano, Dolores Esquivel, Francisco J. Romero-Salguero, César Jiménez-Sanchidrián and José Rafael Ruiz

Catalysts 2022, 12(6), 629; https://doi.org/10.3390/catal12060629 - 08 Jun 2022

Viewed by 1608

Abstract

The development of effective, environmentally friendly catalysts for the Baeyer–Villiger reaction is becoming increasingly important in applied catalysis. In this work, we synthesized a 3D composite consisting of silica spheres coated with Mg/Al hydrotalcite with much better textural properties than its 2D counterparts. In fact, the 3D solid outperformed a 2D-layered hydrotalcite as catalyst in the Baeyer–Villiger reaction of cyclic ketones with H₂O₂/benzonitrile as oxidant. The 3D catalyst provided excellent conversion and selectivity; it was also readily filtered off the reaction mixture. The proposed reaction mechanism, which involves adsorption of the reactants on the hydrotalcite surface, is consistent with the catalytic activity results. Full article

(This article belongs to the Special Issue Nano-Porous Materials for Catalytic Systems in Green Chemistry Processes)

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17 pages, 4938 KiB

Open AccessArticle

Conversion of Weathered Coal into High Value-Added Humic Acid by Magnetically Recoverable Fe₃O₄/LaNiO₃ Nanocatalysts under Solid-Phase Grinding Conditions

by Manrong Song, Gang Wang, Yanli Suo, Zhiqiang Wu, Haijuan Zhan and Wanyi Liu

Catalysts 2022, 12(4), 392; https://doi.org/10.3390/catal12040392 - 31 Mar 2022

Cited by 4 | Viewed by 2017

Abstract

The Fe₃O₄/LaNiO₃ composite, synthesised with the sol-gel method, is considered to be an excellent nanocatalyst for the production of high value-added humic acids from oxidised weathered coal under solid phase milling process conditions. Under optimum process conditions (1% catalyst, 10% activator, 60 min grinding), 48.4% of the weathered coal can be oxidised to produce humic acid. The prepared Fe₃O₄/LaNiO₃ catalyst was characterized by HRTEM, XRD, and XPS, etc. The heterojunction structure that can promote the electron transfer between the components of the composite material was formed with the recombination of Fe₃O₄ and LaNiO₃. The activation of surface oxygen species and adsorbed oxygen could be enhanced with the help of electron transfer between components. Compared to the blank sample or the LaNiO₃ catalyst alone, the molecular weight of the humic acid produced using the Fe₃O₄/LaNiO₃ composite catalyst was significantly lower (maximum heavy mean molecular weight decreased from 59.7 kDa to 5.5 kDa) and the number of reactive groups in humic acid increased (to seven times that of the blank sample). Oxygen-free vacuum experiments indicated that O₂ has an indispensable effect on its excellent catalytic performance in the Fe₃O₄/LaNiO₃ system. In addition, Fe₃O₄/LaNiO₃ could be used at least six times by simple magnetic separation. The development and preparation of perovskite composite catalysts provide a promising approach to the environmentally friendly development and application of weathered coal, as well as an effective method to resolve the associated environmental pollution. Full article

(This article belongs to the Special Issue Nano-Porous Materials for Catalytic Systems in Green Chemistry Processes)

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21 pages, 3334 KiB

Open AccessArticle

Effect of Reaction Time and Hydrothermal Treatment Time on the Textural Properties of SBA-15 Synthesized Using Sodium Silicate as a Silica Source and Its Efficiency for Reducing Tobacco Smoke Toxicity

by Nerea Juárez-Serrano, Desiré Berenguer, Isabel Martínez-Castellanos, Inmaculada Blasco, Maribel Beltrán and Antonio Marcilla

Catalysts 2021, 11(7), 808; https://doi.org/10.3390/catal11070808 - 30 Jun 2021

Cited by 3 | Viewed by 1711

Abstract

The synthesis of SBA-15 has been optimized using sodium silicate, an inexpensive precursor of SBA-15. In this work, the influence of synthesis times of the precipitation and the hydrothermal treatment steps, on the textural properties developed as well as for reducing the toxic compounds generated in tobacco smoking, has been studied. The hydrothermal treatment has been proved to be necessary to obtain materials with adequate performance in this particular application. Twenty-four hours of hydrothermal treatment provide materials with the best properties. Although the reaction stage usually involves the mixing of reagents during 24 h, 40 min is enough to obtain a material with stick-like morphology and typical textural properties. Moreover, between 1 and 2 h of reaction time, the material proved to have the best performance for the purpose of reducing the toxicity of the products generated during the tobacco smoking process. These results are of great significance for an eventual scaling up to industrial scale of the SBA-15 manufacturing process. Results of a pilot plant experiment in a batch of 4 kg of SBA-15 are reported. Full article

(This article belongs to the Special Issue Nano-Porous Materials for Catalytic Systems in Green Chemistry Processes)

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19 pages, 6922 KiB

Open AccessArticle

Continuous 2-Methyl-3-butyn-2-ol Selective Hydrogenation on Pd/γ-Al₂O₃ as a Green Pathway of Vitamin A Precursor Synthesis

by Antonio J. Fernández-Ropero, Bartosz Zawadzki, Emil Kowalewski, Izabela S. Pieta, Mirosław Krawczyk, Krzysztof Matus, Dmytro Lisovytskiy and Anna Śrębowata

Catalysts 2021, 11(4), 501; https://doi.org/10.3390/catal11040501 - 15 Apr 2021

Cited by 10 | Viewed by 2537

Abstract

In this work, the effect of pretreatment conditions (10% H₂/Ar flow rate 25 mL/min and 400 °C, 3 h or 600 °C, 17 h) on the catalytic performance of 1 wt.% Pd/γ-Al₂O₃ has been evaluated for hydrogenation of 2-methyl-3-butyn-2-ol in continuous-flow mode. Two palladium catalysts have been tested under different conditions of pressure and temperature and characterized using various physicochemical techniques. The catalytic performance of red(400 °C)-Pd/γ-Al₂O₃ and red(600 °C)-Pd/γ-Al₂O₃ are affected by the coexistence of several related factors like the competition between PdH and PdCx formation during the reaction, structure sensitivity, hydrogen spillover to the alumina support and presence or absence of Pd–Al species. High-temperature reduction leads to formation of Pd–Al species in addition to pure Pd. The Pd–Al species which reveal unique electronic properties by decreasing the Pd^δ− surface concentration via electron transfer from Pd to Al, leading to a weaker Pd–Alkyl bonding, additionally assisted by the hydrogen spillover, are the sites of improved semi-hydrogenation of 2-methyl-3-butyn-2-ol towards 2-methyl-3-buten-2-ol (97%)—an important intermediate for vitamin A synthesis. Full article

(This article belongs to the Special Issue Nano-Porous Materials for Catalytic Systems in Green Chemistry Processes)

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18 pages, 2149 KiB

Open AccessArticle

Insight into Active Centers and Anti-Coke Behavior of Niobium-Containing SBA-15 for Glycerol Dehydration

by Katarzyna Stawicka, Maciej Trejda and Maria Ziolek

Catalysts 2021, 11(4), 488; https://doi.org/10.3390/catal11040488 - 11 Apr 2021

Cited by 3 | Viewed by 2040

Abstract

Niobium containing SBA-15 was prepared by two methods: impregnation with different amounts of ammonium niobate(V) oxalate (Nb-15/SBA-15 and Nb-25/SBA-15 containing 15 wt.% and 25 wt.% of Nb, respectively) and mixing of mesoporous silica with Nb₂O₅ followed by heating at 500 °C (Nb₂O₅/SBA-15). The use of these two procedures allowed obtaining materials with different textural/surface properties determined by N₂ adsorption/desorption isotherms, XRD, UV-Vis, pyridine, and NO adsorption combined with FTIR spectroscopy. Nb₂O₅/SBA-15 contained exclusively crystalline Nb₂O₅ on the SBA-15 surface, whereas the materials prepared by impregnation had both metal oxide and niobium incorporated into the silica matrix. The niobium species localized in silica framework generated Brønsted (BAS) and Lewis (LAS) acid sites. The inclusion of niobium into SBA-15 skeleton was crucial for the achievement of high catalytic performance. The strongest BAS were on Nb-25/SBA-15, whereas the highest concentration of BAS and LAS was on Nb-15/SBA-15 surface. Nb₂O₅/SBA-15 material possessed only weak LAS and BAS. The presence of the strongest BAS (Nb-25/SBA-15) resulted in the highest dehydration activity, whereas a high concentration of BAS was unfavorable. Silylation of niobium catalysts prepared by impregnation reduced the number of acidic sites and significantly increased acrolein yield and selectivity (from ca. 43% selectivity for Nb-25/SBA-15 to ca. 61% for silylated sample). This was accompanied by a considerable decrease in coke formation (from 47% selectivity for Nb-25/SBA-15 to 27% for silylated material). Full article

(This article belongs to the Special Issue Nano-Porous Materials for Catalytic Systems in Green Chemistry Processes)

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12 pages, 2151 KiB

Open AccessArticle

Structure-Catalytic Properties Relationship in Friedel Crafts Alkylation Reaction for MCM-36-Type Zeolites Obtained by Isopropanol-Assisted Pillaring

by Karolina Ogorzały, Agnieszka Węgrzyn, Aleksandra Korzeniowska, Andrzej Sławek, Andrzej Kowalczyk, Barbara Gil, Wiesław J. Roth and Wacław Makowski

Catalysts 2021, 11(3), 299; https://doi.org/10.3390/catal11030299 - 25 Feb 2021

Cited by 3 | Viewed by 2580

Abstract

MWW type zeolites are characterized by the presence of zeolitic layers of 2.5 nm thickness, containing 10-member ring sinusoidal channels inside and supercavities with 12-member ring openings located on their surfaces. Expansion and pillaring of layered zeolites increase the access to active sites and can enable or facilitate catalytic activity towards larger reactant molecules. This goal is explored in this work reporting the pillaring of layered zeolite MCM-56 with MWW topology by tetraethylorthosilicate (TEOS) treatment with the assistance of isopropanol, aimed at obtaining hierarchical micro-mesoporous systems. MCM-56 (Si/Al = 12) was synthesized with hexamethyleneimine as a structure-directing and aniline as a structure-promoting agent. Hierarchical porous systems were obtained using two different pillaring methods: (1) with TEOS only and (2) with TEOS mixed with isopropanol. The MWW framework was preserved during swelling/pillaring in both methods. Pillared zeolites obtained via alcohol-assisted pillaring possessed unique intermediate micro-mesopores with the size of about 2 nm. IR study revealed a decrease in the concentration of accessible acid centers upon pillaring. However, the fraction of acid sites on the external surface, accessible for adsorption of large molecules, increased by up to 90%. Catalytic activity was evaluated in the Friedel-Crafts alkylation of mesitylene with benzyl alcohol. Pillaring resulted in reduction of the acid site concentrations, but the materials retained high catalytic activity. Pillaring in the presence of alcohol produced increased turnover frequency values based on the concentrations of the external acid sites. Full article

(This article belongs to the Special Issue Nano-Porous Materials for Catalytic Systems in Green Chemistry Processes)

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Review

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21 pages, 403 KiB

Open AccessFeature PaperEditor’s ChoiceReview

Synthesis and Specific Properties of the Ceria and Ceria-Zirconia Nanocrystals and Their Aggregates Showing Outstanding Catalytic Activity in Redox Reactions—A Review

by Roman Dziembaj, Marcin Molenda and Lucjan Chmielarz

Catalysts 2023, 13(8), 1165; https://doi.org/10.3390/catal13081165 - 29 Jul 2023

Cited by 3 | Viewed by 1275

Abstract

Non-stoichiometric CeO_2−y, especially in the form of nanocrystal aggregates, exhibits exceptional catalytic activity in redox reactions. It significantly improves the activity of transition metals and their oxides dispersed on/or in it, also acting as an oxygen buffer. Particularly, active oxygen species (O₂ⁿ⁻, O⁻) are generated at the M/CeO_2−y nanoparticle interface, as well as in the surface layer of their solid-state solutions M_xCe_1−xO_2−y. The crystal structure of CeO₂, ZrO₂ and (Ce, Zr)O₂ and its defects are discussed in connection with the resulting specific catalytic activity. All the methods (simple precipitation and co-precipitation from mother liquors, sol–gel methods, precipitation from nanoemulsions, hydrothermal and solvothermal techniques, combustion and flame spray pyrolysis, precipitation using molecular and solid-state matrices, 3D printing and mechanochemical methods) used for the synthesis of these nanomaterials are comprehensively reviewed, describing the rules of individual procedures and preparation details. Methods of deposition of metal catalysts and their oxides on CeO₂ nanoparticles, such as impregnation, washcoating and precipitation deposition, were also discussed. This review contains more than 160 references to representative papers wherein the reader can find further details on individual syntheses of effective ceria-based catalysts for redox reactions. Full article

(This article belongs to the Special Issue Nano-Porous Materials for Catalytic Systems in Green Chemistry Processes)

28 pages, 5405 KiB

Open AccessFeature PaperReview

Engineering Heterostructures of Layered Double Hydroxides and Metal Nanoparticles for Plasmon-Enhanced Catalysis

by Diana Gilea, Radu G. Ciocarlan, Elena M. Seftel, Pegie Cool and Gabriela Carja

Catalysts 2022, 12(10), 1210; https://doi.org/10.3390/catal12101210 - 11 Oct 2022

Cited by 1 | Viewed by 1957

Abstract

Artificially designed heterostructures formed by close conjunctions of plasmonic metal nanoparticles (PNPs) and non-plasmonic (2D) lamellar nanostructures are receiving extensive interest. The synergistic interactions of the nanounits induce the manifestation of localized surface plasmon resonance (LSPR) in plasmonic metals in the specific environment of the 2D-light absorbing matrix, impacting their potential in plasmon enhanced catalysis. Specifically, layered double hydroxides (LDH) with the advantages of their unique 2D-layered structure, tuned optical absorption, ease of preparation, composition diversity, and high surface area, have emerged as very promising candidates for obtaining versatile and robust catalysts. In this review, we cover the available PNPs/LDH heterostructures, from the most used noble-metals plasmonic of Au and Ag to the novel non-noble-metals plasmonic of Cu and Ni, mainly focusing on their synthesis strategies toward establishing a synergistic response in the coupled nanounits and relevant applications in plasmonic catalysis. First, the structure–properties relationship in LDH, establishing the desirable features of the 2D-layered matrix facilitating photocatalysis, is shortly described. Then, we address the recent research interests toward fabrication strategies for PNPs/support heterostructures as plasmonic catalysts. Next, we highlight the synthesis strategies for available PNPs/LDH heterostructures, how these are entangled with characteristics that enable the manifestation of the plasmon-induced charge separation effect (PICS), co-catalytic effect, or nanoantenna effect in plasmonic catalysis with applications in energy related and environmental photocatalysis. Finally, some perspectives on the challenges and future directions of PNPs/LDHs heterostructures to improve their performance as plasmonic catalysts are discussed. Full article

(This article belongs to the Special Issue Nano-Porous Materials for Catalytic Systems in Green Chemistry Processes)

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74 pages, 7844 KiB

Open AccessReview

Titania-Clay Mineral Composites for Environmental Catalysis and Photocatalysis

by Ewa M. Serwicka

Catalysts 2021, 11(9), 1087; https://doi.org/10.3390/catal11091087 - 09 Sep 2021

Cited by 11 | Viewed by 3737

Abstract

The use of titania-based composite materials in the field of heterogeneous catalysis and photocatalysis has a long and rich history. Hybrid structures combining titania nanoparticles with clay minerals have been extensively investigated for nearly four decades. The attractiveness of clay minerals as components of functional materials stems primarily from their compositional versatility and the possibility of using silicate lamellae as prefabricated building blocks ready to be fitted into the desired nanoconstruction. This review focuses on the evolution over the years of synthetic strategies employed for the manufacturing of titania–clay mineral composites with particular attention to the role of the adopted preparative approach in shaping the physical and chemical characteristics of the materials and enabling, ultimately, tuning of their catalytic and/or photocatalytic performance. Full article

(This article belongs to the Special Issue Nano-Porous Materials for Catalytic Systems in Green Chemistry Processes)

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26 pages, 3231 KiB

Open AccessFeature PaperReview

Modified Layered Silicas as Catalysts for Conversion of Nitrogen Pollutants in Flue Gases—A Review

by Lucjan Chmielarz and Roman Dziembaj

Catalysts 2021, 11(5), 644; https://doi.org/10.3390/catal11050644 - 19 May 2021

Cited by 10 | Viewed by 2616

Abstract

This paper is focused on the recent achievements in the studies of modified layered zeolites and cationic layered clay minerals. These materials are very promising catalysts in green chemistry processes, such as selective catalytic reduction of NO_x with ammonia (NH₃-SCR) and selective catalytic oxidation of ammonia to dinitrogen (NH₃-SCO). Special attention is paid to the roles of the micro- and mesoporous structures of the catalytic materials, the type and location of deposited transition metals, as well as surface acidity in the design of effective catalysts for the NH₃-SCR and NH₃-SCO processes. The majority of the presented analysis is based on the authors’ research. Full article

(This article belongs to the Special Issue Nano-Porous Materials for Catalytic Systems in Green Chemistry Processes)

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39 pages, 11070 KiB

Open AccessFeature PaperReview

Porous Silica-Based Organic-Inorganic Hybrid Catalysts: A Review

by Andrea Erigoni and Urbano Diaz

Catalysts 2021, 11(1), 79; https://doi.org/10.3390/catal11010079 - 08 Jan 2021

Cited by 29 | Viewed by 4899

Abstract

Hybrid organic-inorganic catalysts have been extensively investigated by several research groups in the last decades, as they allow combining the structural robust-ness of inorganic solids with the versatility of organic chemistry. Within the field of hybrid catalysts, synthetic strategies based on silica are among the most exploitable, due to the convenience of sol-gel chemistry, to the array of silyl-derivative precursors that can be synthesized and to the number of post-synthetic functionalization strategies available, amongst others. This review proposes to highlight these advantages, firstly describing the most common synthetic tools and the chemistry behind sol-gel syntheses of hybrid catalysts, then presenting exemplificative studies involving mono- and multi-functional silica-based hybrid catalysts featuring different types of active sites (acid, base, redox). Materials obtained through different approaches are described and their properties, as well as their catalytic performances, are compared. The general scope of this review is to gather useful information for those approaching the synthesis of organic-inorganic hybrid materials, while providing an overview on the state-of-the art in the synthesis of such materials and highlighting their capacities. Full article

(This article belongs to the Special Issue Nano-Porous Materials for Catalytic Systems in Green Chemistry Processes)

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