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Porous and Nanoporous Materials in Heterogeneous Catalysis
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Porous and Nanoporous Materials in Heterogeneous Catalysis

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Materials Chemistry".

Deadline for manuscript submissions: 30 June 2025 | Viewed by 5328

Special Issue Editor

Dr. Angela Martins

E-Mail Website
Guest Editor
Department of Chemical Engineering, Instituto Superior de Engenharia de Lisboa, 1950-007 Lisboa, Portugal
Interests: heterogeneous catalysis; zeolites; hierarchical zeolites; bifunctional catalysts; carbon materials; porous silicas
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Porous and nanoporous materials have a wide range of applications in molecular separation, adsorption, and especially as heterogeneous catalysts or catalyst supports. A large set of porous materials such as zeolites and zeotypes, metal organic frameworks (MOFs), carbon materials, and mesoporous silicas have in common the presence of a large surface area and pore volume. The micropores inside such materials can act as microreactors, where the native active sites or introduced species, such as metals, promote the occurrence of catalytic reactions. On the other hand, larger pores or even the external surface of these materials can accommodate bulky species such as enzymes or organometallic catalysts, preventing leaching and transforming homogenous catalysts to environmentally friendly and reusable heterogeneous catalysts.

The aim of this Special Issue is to generate discussion concerning the synthesis and modification of porous and nanoporous materials, focusing on their applications as catalysts or catalyst supports for heterogeneous catalysis.

Dr. Angela Martins
Guest Editor

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

  • porous and nanoporous materials
  • heterogeneous catalysts
  • hierarchical materials
  • bifunctional catalysts
  • catalyst supports
  • zeolites
  • zeotypes
  • carbon materials
  • MOFs
  • mesoporous silicas

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Published Papers (5 papers)

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Research

12 pages, 3285 KiB  
Article
CO2 Hydrogenation to Methanol over In2O3 Decorated by Metals of the Iron Triad
by Tomáš Stryšovský, Martina Kajabová, Arkadii Bikbashev, Zuzana Kovářová, Radka Pocklanová, Robert Prucek, Aleš Panáček, Josef Kašlík, Martin Petr and Libor Kvítek
Molecules 2024, 29(22), 5325; https://doi.org/10.3390/molecules29225325 - 12 Nov 2024
Viewed by 443
Abstract
The growing concentration of CO2 in the atmosphere is a serious problem, and efforts to counter this issue are thus highly important. One of the possible approaches to solving this problem is the conversion of waste CO2 into products with added [...] Read more.
The growing concentration of CO2 in the atmosphere is a serious problem, and efforts to counter this issue are thus highly important. One of the possible approaches to solving this problem is the conversion of waste CO2 into products with added economic value. Methanol is one of these products with vast potential usage. In this study, indium oxide prepared by a simple precipitation method and modified by nanoparticles of metals from the iron triad were tested as possible catalysts to produce methanol by the method of CO2 hydrogenation. The prepared catalysts demonstrated a strong dependence of their catalytic activity on used metal. The best selectivity for the production of CH3OH was observed for the Fe/In2O3 catalyst at the value of 54.7% at 300 °C. However, due to the higher value of CO2 conversion, the highest CH3OH formation rate was observed at a value of 11.3 mmol/(h*g) at 300 °C for a composite of Ni/In2O3. Full article
(This article belongs to the Special Issue Porous and Nanoporous Materials in Heterogeneous Catalysis)
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24 pages, 4924 KiB  
Article
Thermal and/or Microwave Treatment: Insight into the Preparation of Titania-Based Materials for CO2 Photoreduction to Green Chemicals
by Iwona Pełech, Daniel Sibera, Piotr Staciwa, Konrad Sobczuk, Ewelina Kusiak-Nejman, Agnieszka Wanag, Antoni W. Morawski, Kenneth Schneider, Richard Blom and Urszula Narkiewicz
Molecules 2024, 29(15), 3646; https://doi.org/10.3390/molecules29153646 - 1 Aug 2024
Viewed by 892
Abstract
Titanium dioxide was synthesized via hydrolysis of titanium (IV) isopropoxide using a sol–gel method, under neutral or basic conditions, and heated in the microwave-assisted solvothermal reactor and/or high-temperature furnace. The phase composition of the prepared samples was determined using the X-ray diffraction method. [...] Read more.
Titanium dioxide was synthesized via hydrolysis of titanium (IV) isopropoxide using a sol–gel method, under neutral or basic conditions, and heated in the microwave-assisted solvothermal reactor and/or high-temperature furnace. The phase composition of the prepared samples was determined using the X-ray diffraction method. The specific surface area and pore volumes were determined through low-temperature nitrogen adsorption/desorption studies. The photoactivity of the samples was tested through photocatalytic reduction of carbon dioxide. The composition of the gas phase was analyzed using gas chromatography, and hydrogen, carbon oxide, and methane were identified. The influence of pH and heat treatment on the physicochemical properties of titania-based materials during photoreduction of carbon dioxide have been studied. It was found that the photocatalysts prepared in neutral environment were shown to result in a higher content of hydrogen, carbon monoxide, and methane in the gas phase compared to photocatalysts obtained under basic conditions. The highest amounts of hydrogen were detected in the processes using photocatalysts heated in the microwave reactor, and double-heated photocatalysts. Full article
(This article belongs to the Special Issue Porous and Nanoporous Materials in Heterogeneous Catalysis)
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19 pages, 2869 KiB  
Article
Modification of Silica with Sucrose and Ammonium Fluoride Agents: A Facile Route to Prepare Supports of Iridium Catalysts for Hydrogenation Reaction
by Ewa Janiszewska, Mariusz Pietrowski and Michał Zieliński
Molecules 2024, 29(14), 3430; https://doi.org/10.3390/molecules29143430 - 22 Jul 2024
Viewed by 822
Abstract
Mesoporous silica materials were synthesized using inexpensive and environmentally friendly sucrose as a porogeneous agent. It was found that the presence of sucrose and the products of its chemical transformation during synthesis (e.g., furfural polymer) significantly affected the structure of the obtained porous [...] Read more.
Mesoporous silica materials were synthesized using inexpensive and environmentally friendly sucrose as a porogeneous agent. It was found that the presence of sucrose and the products of its chemical transformation during synthesis (e.g., furfural polymer) significantly affected the structure of the obtained porous silica. The influence of synthesis conditions (pH, temperature, time) on the textural properties of the final materials was determined. Samples obtained in an acidic medium, at pH = 1, and treated at room temperature, yielded products with a large surface area and a narrow pore size distribution in the range of 2–5 nm, while the synthesis at pH = 8 allowed for the formation of mesoporous systems with pores in the range of 14–20 nm. To generate acidity, the silicas were modified with an ammonium fluoride solution and then used as supports for iridium catalysts in a hydrogenation reaction, with toluene as a model hydrocarbon. The influence of parameters such as specific surface area, support acidity, and iridium dispersion on catalytic activity was determined. It was shown that modification with sucrose improved the porous structure, and NH4F modification generated acidity. These parameters favored better reducibility and dispersion of the active phase, resulting in higher activity of the catalysts in the studied hydrogenation reaction. Full article
(This article belongs to the Special Issue Porous and Nanoporous Materials in Heterogeneous Catalysis)
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16 pages, 3122 KiB  
Article
Thiophene-Based Covalent Triazine Frameworks as Visible-Light-Driven Heterogeneous Photocatalysts for the Oxidative Coupling of Amines
by Manuel Melero, Urbano Díaz and Francesc X. Llabrés i Xamena
Molecules 2024, 29(7), 1637; https://doi.org/10.3390/molecules29071637 - 5 Apr 2024
Viewed by 1527
Abstract
This study reports on a metal-free Covalent Triazine Framework (CTF) incorporating bithiophene structural units (TP-CTF) with a semicrystalline structure as an efficient heterogeneous photocatalyst under visible light irradiation. The physico-chemical properties and composition of this material was confirmed via different characterization solid-state techniques, [...] Read more.
This study reports on a metal-free Covalent Triazine Framework (CTF) incorporating bithiophene structural units (TP-CTF) with a semicrystalline structure as an efficient heterogeneous photocatalyst under visible light irradiation. The physico-chemical properties and composition of this material was confirmed via different characterization solid-state techniques, such as XRD, TGA, CO2 adsorption and FT-IR, NMR and UV-Vis spectroscopies. The compound was synthesized through a solvothermal process and was explored as a heterogeneous photocatalyst for the oxidative coupling of amines to imines under visible light irradiation. TP-CTF demonstrated outstanding photocatalytic activity, with high conversion rates and selectivity. Importantly, the material exhibited exceptional stability and recyclability, making it a strong candidate for sustainable and efficient imine synthesis. The low bandgap of TP-CTF enabled the efficient absorption of visible light, which is a notable advantage for visible-light-driven photocatalysis. Full article
(This article belongs to the Special Issue Porous and Nanoporous Materials in Heterogeneous Catalysis)
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15 pages, 2720 KiB  
Article
Hierarchical Zeolites Prepared Using a Surfactant-Mediated Strategy: ZSM-5 vs. Y as Catalysts for Friedel–Crafts Acylation Reaction
by Angela Martins, Beatriz Amaro, M. Soledade C. S. Santos, Nelson Nunes, Ruben Elvas-Leitão and Ana P. Carvalho
Molecules 2024, 29(2), 517; https://doi.org/10.3390/molecules29020517 - 20 Jan 2024
Cited by 3 | Viewed by 1259
Abstract
Hierarchical ZSM5 and Y zeolites were prepared through a surfactant-mediated strategy with NH4OH changing the duration of the treatment and the amount of CTAB surfactant and taking as reference multiples of the critical micellar concentration (CMC). The materials were characterized using [...] Read more.
Hierarchical ZSM5 and Y zeolites were prepared through a surfactant-mediated strategy with NH4OH changing the duration of the treatment and the amount of CTAB surfactant and taking as reference multiples of the critical micellar concentration (CMC). The materials were characterized using powder X-ray diffraction, N2 adsorption isotherms at −196 °C, and SEM and TEM microscopy. The catalytic performance was evaluated in Friedel–Crafts acylation of furan with acetic anhydride at 80 °C. The alkaline surfactant-mediated treatment had different effects on the two zeolites. For ZSM5, the CTAB molecular aggregates can hardly diffuse inside the medium-size pores, leading mainly to intercrystalline mesoporosity and increased external surface area, with no positive catalytic impact. On the other hand, for large-pore Y zeolite, the CTAB molecular aggregates can easily diffuse and promote the rearrangement of crystal units around micelles, causing the enlargement of the pores, i.e., intracrystalline porosity. The optimized Y-based sample, treated for 12 h with a CTAB amount 32 times the CMC, shows an increase in product yield and rate constant that was not observed when a higher amount of surfactant was added. The reuse of spent catalysts upon thermal treatment at 400 °C shows a regeneration efficiency around 90%, showing good potentialities for the modified catalysts. Full article
(This article belongs to the Special Issue Porous and Nanoporous Materials in Heterogeneous Catalysis)
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