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Advances in Microporous and Mesoporous Materials

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A special issue of Materials (ISSN 1996-1944). This special issue belongs to the section "Porous Materials".

Deadline for manuscript submissions: closed (31 May 2021) | Viewed by 32974

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Special Issue Editor

Prof. Dr. Pascal Van Der Voort

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Guest Editor

Department of Chemistry, Center for Ordered Materials, Organometallics and Catalysis (COMOC), Faculty of Sciences, Ghent University, Krijgslaan 281 (S3), 9000 Ghent, Belgium
Interests: ordered mesostructures; metal organic frameworks (MOFs); periodic mesoporous organosilicas; covalent organic frameworks; adsorption; catalysis and catalytic materials

Special Issue Information

Dear Colleagues,

We are experiencing exciting times in the field of microporous and mesoporous materials. After the revolution in 1992 caused by Mobil, we now see how hybrid materials, and even purely organic compounds are quickly finding applications. Furthermore, new materials are being developed every day. I am referring to the MOFs, the PMOs, the COFs, the CTFs, and novel forms of porous and conducting carbons. On the other hand, we should not forget that research on zeolites and mesoporous silica is still very much alive, and even today more papers are published on the topic of zeolites than on the other mentioned materials.

My interest lies in “hybrid materials for sustainability”, but many other applications are exciting, from sensors to dental fillings, from drug carriers to thermochromic materials, next to the highly important fields of catalysis, gas storage and separation, and liquid phase adsorption.

I truly hope you will contribute to this exciting Special Issue of Materials, as we celebrate 20 years of MOFs and PMOs, which both broke through in 1999.

Prof. Pascal Van Der Voort
Guest Editor

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. Materials is an international peer-reviewed open access semimonthly 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 2600 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

hybrid materials
MOF
COF
CTF
PMO
carbon
zeolite
ordered materials
new materials
sustainability
sensors
catalysis
adsorption

Published Papers (11 papers)

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Research

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13 pages, 10780 KiB

Open AccessEditor’s ChoiceArticle

Covalent Triazine Frameworks Based on the First Pseudo-Octahedral Hexanitrile Monomer via Nitrile Trimerization: Synthesis, Porosity, and CO₂ Gas Sorption Properties

by Isabelle D. Wessely, Alexandra M. Schade, Subarna Dey, Asamanjoy Bhunia, Alexander Nuhnen, Christoph Janiak and Stefan Bräse

Materials 2021, 14(12), 3214; https://0-doi-org.brum.beds.ac.uk/10.3390/ma14123214 - 10 Jun 2021

Cited by 9 | Viewed by 2570

Abstract

Herein, we report the first synthesis of covalent triazine-based frameworks (CTFs) based on a hexanitrile monomer, namely the novel pseudo-octahedral hexanitrile 1,4-bis(tris(4′-cyano-phenyl)methyl)benzene 1 using both ionothermal reaction conditions with ZnCl₂ at 400 °C and the milder reaction conditions with the strong Brønsted acid trifluoromethanesulfonic acid (TFMS) at room temperature. Additionally, the hexanitrile was combined with different di-, tri-, and tetranitriles as a second linker based on recent work of mixed-linker CTFs, which showed enhanced carbon dioxide captures. The obtained framework structures were characterized via infrared (IR) spectroscopy, elemental analysis, scanning electron microscopy (SEM), and gas sorption measurements. Nitrogen adsorption measurements were performed at 77 K to determine the Brunauer-Emmett-Teller (BET) surface areas range from 493 m²/g to 1728 m²/g (p/p₀ = 0.01–0.05). As expected, the framework CTF-hex6 synthesized from 1 with ZnCl₂ possesses the highest surface area for nitrogen adsorption. On the other hand, the mixed framework structure CTF-hex4 formed from the hexanitrile 1 and 1,3,5 tricyanobenzene (4) shows the highest uptake of carbon dioxide and methane of 76.4 cm³/g and 26.6 cm³/g, respectively, at 273 K. Full article

(This article belongs to the Special Issue Advances in Microporous and Mesoporous Materials)

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19 pages, 3330 KiB

Open AccessArticle

Study on Porosity in Zinc Oxide Ultrathin Films from Three-Step MLD Zn-Hybrid Polymers

by Richard Berger, Martin Seiler, Alberto Perrotta and Anna Maria Coclite

Materials 2021, 14(6), 1418; https://0-doi-org.brum.beds.ac.uk/10.3390/ma14061418 - 15 Mar 2021

Cited by 3 | Viewed by 1586

Abstract

Deriving mesoporous ZnO from calcinated, molecular layer deposited (MLD) metal-organic hybrid thin films offers various advantages, e.g., tunable crystallinity and porosity, as well as great film conformality and thickness control. However, such methods have barely been investigated. In this contribution, zinc-organic hybrid layers were for the first time formed via a three-step MLD sequence, using diethylzinc, ethanolamine, and maleic anhydride. These zinc-organic hybrid films were then calcinated with the aim of enhancing the porosity of the obtained ZnO films. The saturation curves for the three-step MLD process were measured, showing a growth rate of 4.4 ± 0.2 Å/cycle. After initial degradation, the zinc-organic layers were found to be stable in ambient air. The transformation behavior of the zinc-organic layers, i.e., the evolution of the film thickness and refractive index as well as the pore formation upon heating to 400, 500, and 600 °C were investigated with the help of spectroscopic ellipsometry and ellipsometric porosimetry. The calculated pore size distribution showed open porosity values of 25%, for the sample calcinated at 400 °C. The corresponding expectation value for the pore radius obtained from this distribution was 2.8 nm. Full article

(This article belongs to the Special Issue Advances in Microporous and Mesoporous Materials)

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12 pages, 9740 KiB

Open AccessArticle

Nitrogen-Doped Hierarchical Porous Activated Carbon Derived from Paddy for High-Performance Supercapacitors

by Yudan Yuan, Yi Sun, Zhichen Feng, Xingjian Li, Ruowei Yi, Wei Sun, Cezhou Zhao and Li Yang

Materials 2021, 14(2), 318; https://0-doi-org.brum.beds.ac.uk/10.3390/ma14020318 - 09 Jan 2021

Cited by 22 | Viewed by 2985

Abstract

A facile and environmentally friendly fabrication is proposed to prepare nitrogen-doped hierarchical porous activated carbon via normal-pressure popping, one-pot activation and nitrogen-doping process. The method adopts paddy as carbon precursor, KHCO₃ and dicyandiamide as the safe activating agent and nitrogen dopant. The as-prepared activated carbon presents a large specific surface area of 3025 m²·g⁻¹ resulting from the synergistic effect of KHCO₃ and dicyandiamide. As an electrode material, it shows a maximum specific capacitance of 417 F·g⁻¹ at a current density of 1 A·g⁻¹ and very good rate performance. Furthermore, the assembled symmetric supercapacitor presents a large specific capacitance of 314.6 F·g⁻¹ and a high energy density of 15.7 Wh·Kg⁻¹ at 1 A·g⁻¹, maintaining 14.4 Wh·Kg⁻¹ even at 20 A·g⁻¹ with the energy density retention of 91.7%. This research demonstrates that nitrogen-doped hierarchical porous activated carbon derived from paddy has a significant potential for developing a high-performance renewable supercapacitor and provides a new route for economical and large-scale production in supercapacitor application. Full article

(This article belongs to the Special Issue Advances in Microporous and Mesoporous Materials)

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10 pages, 1405 KiB

Open AccessArticle

Beneficial Use of MIBC in Metakaolin-Based Geopolymers to Improve Flowability and Compressive Strength

by Sujeong Lee, Byoungkwan Kim, Joobeom Seo and Shinhu Cho

Materials 2020, 13(17), 3663; https://0-doi-org.brum.beds.ac.uk/10.3390/ma13173663 - 19 Aug 2020

Cited by 13 | Viewed by 2245

Abstract

Superplasticizers (cement concrete water reducers) are applied to improve the flowability of calcium-rich, alkali-activated materials, with inconsistent results. However, superplasticizer applications are limited in metakaolin-based geopolymers. The possibility of using polycarboxylate superplasticizers and methyl isobutyl carbinol (MIBC) to ameliorate the flowability of metakaolin-based geopolymers was investigated. The ratio of metakaolin, fumed silica, NaOH or KOH, and water in geopolymers at a Na₂O or K₂O:Al₂O₃:SiO₂:H₂O ratio = 1:1:4:10 or 1:1:4:11 was maintained in the formulations. In this study, ether- or ester-based polycarboxylate superplasticizers did not improve the workability of fresh metakaolin-based Na-geopolymers. A low MIBC dose (0.5 wt.% of metakaolin) improved the flowability by 19% and additionally increased the 7-day compressive strength by 22% from 68 to 83 MPa for plain Na-geopolymers. The entrained fine froths produced by adding MIBC during mixing likely reduced friction between metakaolin particles, and the slurry became more workable. Hence, the geopolymer mixture with an improved flowability became more homogenous, which ensured more extensive metakaolin dissolution and hydrolysis. A low MIBC dose could be effective for Na-geopolymers with dual benefits of improved workability and enhanced compressive strength. Full article

(This article belongs to the Special Issue Advances in Microporous and Mesoporous Materials)

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12 pages, 3892 KiB

Open AccessArticle

Synthesis and Characterization of Novel Pyridine Periodic Mesoporous Organosilicas and Its Catalytic Activity in the Knoevenagel Condensation Reaction

by Fatemeh Rajabi, Arezoo Zare Ebrahimi, Ahmad Rabiee, Antonio Pineda and Rafael Luque

Materials 2020, 13(5), 1097; https://0-doi-org.brum.beds.ac.uk/10.3390/ma13051097 - 02 Mar 2020

Cited by 13 | Viewed by 2810

Abstract

The preparation of novel organic-inorganic hybrid mesoporous organosilica containing pyridinedicarboxamide functional groups uniformly distributed inside the nanostructured pore walls has been addressed. The mesoporosity and uniformity of the synthesized nanomaterials were characterized by different techniques such as nitrogen adsorption/desorption measurements and powder X-ray diffraction (PXRD). Additionally, the presence of the pyridinedicarboxamide in the pore walls of the nanomaterials was assessed by Fourier-transform infrared spectroscopy (FT-IR), as well as ²⁹Si and ¹³C solid-state cross-polarization and magic angle spinning nuclear magnetic resonance (CP/MAS-NMR). The Knoevenagel condensation of aldehydes with active methylene compounds was carried out over the pyridinedicarboxamide functionalized mesoporous organosilica, which has been proven to be an efficient heterogeneous basic catalyst in the presence of ethanol as solvent. The catalytic activity of the investigated materials was investigated in the Knoevenagel condensation between malononitrile and several benzaldehyde derivatives exhibiting a high conversion (>90%) and excellent selectivity toward the final condensation products under very mild reaction conditions. Furthermore, the catalyst stability is noteworthy as it could be recycled and reused at least twelve times without any significant change in the performance. Full article

(This article belongs to the Special Issue Advances in Microporous and Mesoporous Materials)

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14 pages, 2551 KiB

Open AccessArticle

Transition Metal Oxodiperoxo Complex Modified Metal-Organic Frameworks as Catalysts for the Selective Oxidation of Cyclohexane

by Yuechao Hong, Jie Peng, Zhichao Sun, Zhiquan Yu, Anjie Wang, Yao Wang, Ying-Ya Liu, Fen Xu and Li-Xian Sun

Materials 2020, 13(4), 829; https://0-doi-org.brum.beds.ac.uk/10.3390/ma13040829 - 12 Feb 2020

Cited by 12 | Viewed by 2798

Abstract

In this work, a series of modified metal-organic frameworks (MOFs) have been prepared by pre- and post-treatment with transition metal oxodiperoxo complexes (MoO(O₂)₂, WO(O₂)₂, and KVO(O₂)₂). The obtained materials are characterized by XRD, FTIR, SEM, TEM, inductively coupled plasma atomic emission spectrometry (ICP-AES), and X-ray photoelectron spectroscopy (XPS), as well as by N₂ adsorption/desorption measurement. The characterization results show that transition metal oxodiperoxo complexes are uniformly incorporated into the MOF materials without changing the basic structures. The performance of cyclohexane oxidation on metal oxodiperoxo complex modified MOFs are evaluated. UiO-67-KVO(O₂)₂ shows the best performance for cyclohexane oxidation, with 78% selectivity to KA oil (KA oil refers to a cyclohexanol and cyclohexanone mixture) at 9.4% conversion. The KA selectivity is found to depend on reaction time, while hot-filtration experiments indicates that the catalytic process is heterogeneous with no leaching of metal species. Full article

(This article belongs to the Special Issue Advances in Microporous and Mesoporous Materials)

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23 pages, 9119 KiB

Open AccessArticle

Monometallic Cerium Layered Double Hydroxide Supported Pd-Ni Nanoparticles as High Performance Catalysts for Lignin Hydrogenolysis

by Tibo De Saegher, Jeroen Lauwaert, Jorku Hanssen, Els Bruneel, Matthias Van Zele, Kevin Van Geem, Klaartje De Buysser and An Verberckmoes

Materials 2020, 13(3), 691; https://0-doi-org.brum.beds.ac.uk/10.3390/ma13030691 - 04 Feb 2020

Cited by 11 | Viewed by 3521

Abstract

Monometallic cerium layered double hydroxides (Ce-LDH) supports were successfully synthesized by a homogeneous alkalization route driven by hexamethylenetetramine (HMT). The formation of the Ce-LDH was confirmed and its structural and compositional properties studied by XRD, SEM, XPS, iodometric analyses and TGA. HT-XRD, N₂-sorption and XRF analyses revealed that by increasing the calcination temperature from 200 to 800 °C, the Ce-LDH material transforms to ceria (CeO₂) in four distinct phases, i.e., the loss of intramolecular water, dehydroxylation, removal of nitrate groups and removal of sulfate groups. When loaded with 2.5 wt% palladium (Pd) and 2.5 wt% nickel (Ni) and calcined at 500 °C, the PdNi-Ce-LDH-derived catalysts strongly outperform the PdNi-CeO₂ benchmark catalyst in terms of conversion as well as selectivity for the hydrogenolysis of benzyl phenyl ether (BPE), a model compound for the α-O-4 ether linkage in lignin. The PdNi-Ce-LDH catalysts showed full selectivity towards phenol and toluene while the PdNi-CeO₂ catalysts showed additional oxidation of toluene to benzoic acid. The highest BPE conversion was observed with the PdNi-Ce-LDH catalyst calcined at 600 °C, which could be related to an optimum in morphological and compositional characteristics of the support. Full article

(This article belongs to the Special Issue Advances in Microporous and Mesoporous Materials)

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14 pages, 3475 KiB

Open AccessArticle

Thiol-Functionalized Ethylene Periodic Mesoporous Organosilica as an Efficient Scavenger for Palladium: Confirming the Homogeneous Character of the Suzuki Reaction

by María I. López, Dolores Esquivel, César Jiménez-Sanchidrián, Pascal Van Der Voort and Francisco J. Romero-Salguero

Materials 2020, 13(3), 623; https://0-doi-org.brum.beds.ac.uk/10.3390/ma13030623 - 30 Jan 2020

Cited by 6 | Viewed by 2666

Abstract

This work describes the synthesis of thiol-functionalized periodic mesoporous organosilicas (PMOs) prepared using the precursor 1-thiol-1,2-bis(triethoxysilyl)ethane, alone or mixed with 1,2-bis(triethoxysilyl)ethane. The thiol groups incorporated into the structure were found to be efficient for palladium binding. This has allowed these materials to be used as catalysts in the Suzuki cross-coupling reaction of bromobenzene and phenylboronic acid. Their performance has been compared to palladium-supported periodic mesoporous (organo)silicas and important differences have been observed between them. The use of different heterogeneity tests, such as hot filtration test and poisoning experiments, has provided a deep insight into the reaction mechanism and has confirmed that the reaction occurs in the homogeneous phase following a “release and catch” mechanism. Furthermore, the thiol-functionalized periodic mesoporous organosilica, synthesized using only 1-thiol-1,2-bis(triethoxysilyl)ethane as a precursor, has proven to be an efficient palladium scavenger. Full article

(This article belongs to the Special Issue Advances in Microporous and Mesoporous Materials)

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18 pages, 4169 KiB

Open AccessFeature PaperArticle

Terbium Ion Adsorption from Aqueous Solution by Using Magnetic γ-Fe₂O₃-NH₄OH@SiO₂ Nanoparticles Functionalized with Amino Groups

by Tina Kegl, Aljoša Košak, Aleksandra Lobnik and Irena Ban

Materials 2019, 12(8), 1294; https://0-doi-org.brum.beds.ac.uk/10.3390/ma12081294 - 19 Apr 2019

Cited by 7 | Viewed by 3803

Abstract

New magnetic stabilized and functionalized core@shell nanoparticles (NPs) were synthesized in a simple way and characterized in order to adsorb Tb³⁺ from aqueous solution with a very low Tb³⁺ concentration. For the fluorescence determination of adsorption efficiency and capacity, tiron monohydrate as a ligand was used. The obtained results confirm the potential of the synthesized magnetic γ-Fe₂O₃-NH₄OH@SiO₂ NPs, functionalized with (3-Aminopropyl) trimethoxysilane (APTMS), to be used for adsorption of Tb³⁺ from aqueous solution, with the possibility of its removal from aqueous solution via an external magnet. The endothermic and spontaneous adsorption follows a pseudo-second-order kinetic model, and the adsorption equilibrium data fit the Temkin isotherm well. The maximum adsorption efficiency from aqueous solution with a 2 × 10⁻⁶ M concentration of Tb³⁺ is over 90% at pH 7. Full article

(This article belongs to the Special Issue Advances in Microporous and Mesoporous Materials)

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Review

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29 pages, 5502 KiB

Open AccessReview

Advances and Challenges in the Creation of Porous Metal Phosphonates

by Bharadwaj Mysore Ramesha and Vera Meynen

Materials 2020, 13(23), 5366; https://0-doi-org.brum.beds.ac.uk/10.3390/ma13235366 - 26 Nov 2020

Cited by 15 | Viewed by 3016

Abstract

In the expansive world of porous hybrid materials, a category of materials that has been rather less explored than others and is gaining attention in development is the porous metal phosphonates. They offer promising features towards applications which demand control over the inorganic–organic network and interface, which is critical for adsorption, catalysis and functional devices and technology. The need to establish a rationale for new synthesis approaches to make these materials in a controlled manner is by itself an important motivation for material chemists. In this review, we highlight the various synthetic strategies exploited, discussing various metal phosphonate systems and how they influence the properties of porous metal phosphonates. We discuss porous metal phosphonate systems based on transition metals with an emphasis on addressing challenges with tetravalent metals. Finally, this review provides a brief description of some key areas of application that are ideally suited for porous metal phosphonates. Full article

(This article belongs to the Special Issue Advances in Microporous and Mesoporous Materials)

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26 pages, 9664 KiB

Open AccessReview

Light-Emitting Lanthanide Periodic Mesoporous Organosilica (PMO) Hybrid Materials

by Anna M. Kaczmarek and Pascal Van Der Voort

Materials 2020, 13(3), 566; https://0-doi-org.brum.beds.ac.uk/10.3390/ma13030566 - 24 Jan 2020

Cited by 21 | Viewed by 3314

Abstract

Periodic mesoporous organosilicas (PMOs) have a well ordered mesoporous structure, a high thermal and mechanical stability and a uniform distribution of organic functionalities in the pore walls. The organic groups allow PMOs to be modified and functionalized by using a wide range of organic reactions. Since their first report in 1999, PMOs have found a vast range of applications, such as for catalysis, adsorbents, low-k films, biomedical supports and also for optical applications. Optical applications are very interesting as PMOs offer the possibility of designing advanced luminescent hybrid materials comprising of organic components, yet with much higher stability and very good processability. Despite their promising possibilities, the optical properties of pristine PMOs and PMOs grafted with d-metal or f-metal ions and complexes have been explored less frequently. In this review, we aimed to overview the exciting light emitting properties of various reported lanthanide PMO hybrid materials and interest the reader in this promising application for lanthanide PMO materials. Full article

(This article belongs to the Special Issue Advances in Microporous and Mesoporous Materials)

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