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Emerging Applications of Metal-Organic Frameworks and Related Porous Materials

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

Deadline for manuscript submissions: closed (15 August 2022) | Viewed by 27915

Special Issue Editors


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Guest Editor
Department of Inorganic Chemistry, University of Valencia, Valencia, Spain
Interests: metal–organic frameworks (MOFs) and their applications; materials chemistry; nanomaterials

E-Mail Website
Guest Editor
University of Valencia, Valencia, Spain
Interests: catalysis, metal–organic frameworks (MOFs) and their applications; materials chemistry

Special Issue Information

Dear Colleagues,

Metal–organic frameworks (MOFs) have attracted much attention in the field of gas storage/separation, catalysts, energy storage, and chemical sensors due to their porous characteristics, wide variety of architectures, and the functionality of their empty space.

This Special Issue will provide an attractive opportunity for the readership to obtain significant and helpful information concerning novel approaches for the synthesis of MOFs (and related porous materials) and their application in different fields of technological interest. This will be an appropriate occasion for the authors to exhibit and publish their latest achievements in this and related fields.

This Special Issue will accept extensive contributions involving all the different aspects broadly indicated by the keywords. Review articles by experts in the field will also be welcomed.

Prof. Dr. Emilio Pardo
Dr. Jesús Ferrando Soria
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

  • metal–organic frameworks
  • porous materials
  • technological applications
  • host–guest chemistry

Published Papers (10 papers)

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Research

Jump to: Review

18 pages, 7106 KiB  
Article
Photocatalytic Degradation of Dyes Using Titania Nanoparticles Supported in Metal-Organic Materials Based on Iron
by Elizabeth Rojas-García, Diana Carolina García-Martínez, Ricardo López-Medina, Fernando Rubio-Marcos, Aldo A. Castañeda-Ramírez and Ana M. Maubert-Franco
Molecules 2022, 27(20), 7078; https://doi.org/10.3390/molecules27207078 - 20 Oct 2022
Cited by 3 | Viewed by 1984
Abstract
Composite materials based on titania nanoparticles (TiO2 NPs) and three metal-organic frameworks (MOFs) called MIL-53 (Fe) ((Fe (III) (OH) (1,4-BDC)), MILs (Materials Institute Lavoisier)), MIL-100 (Fe) (Fe3O(H2O)2OH(BTC)2), and Fe-BTC (iron-benzenetricarboxylate) with different percentages of [...] Read more.
Composite materials based on titania nanoparticles (TiO2 NPs) and three metal-organic frameworks (MOFs) called MIL-53 (Fe) ((Fe (III) (OH) (1,4-BDC)), MILs (Materials Institute Lavoisier)), MIL-100 (Fe) (Fe3O(H2O)2OH(BTC)2), and Fe-BTC (iron-benzenetricarboxylate) with different percentages of TiO2 NPs (0.5, 1, and 2.5% wt.) were synthesized using the solvothermal method and used as photocatalytic materials in the degradation of two dyes (Orange II and Reactive Black 5 (RB5)). The pristine and composite materials were characterized with X-ray diffraction, Raman, UV–Vis and Fourier transform infrared spectroscopy and scanning electron microscopy techniques. The 2.5TiO2/MIL-100 composite material showed the best results for the degradation of both dyes (Reactive Black 5 and Orange II dye, 99% and 99.5% degradation in 105 and 150 min, respectively). The incorporation of TiO2 NPs into MOFs can decrease the recombination of the change carrier in the MOF, increasing the photocatalytic activity of a pristine MOF. Results therefore indicated that the synthesized MOF nanocomposites have good potential for wastewater treatment. Full article
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12 pages, 6142 KiB  
Article
New Generation of MOF-Monoliths Based on Metal Foams
by José J. Delgado-Marín, Dennis P. Izan, Miguel Molina-Sabio, Enrique V. Ramos-Fernandez and Javier Narciso
Molecules 2022, 27(6), 1968; https://doi.org/10.3390/molecules27061968 - 18 Mar 2022
Cited by 12 | Viewed by 2212
Abstract
Herein, it has been developed a method to prepare metallic foams starting from Zamak5 (ZnAlCu alloy) with different pore sizes. The Zamak5 metallic foam is designed to serve as a support and metallic precursor of ZIF-8. In this way, composite materials MOF-metal can [...] Read more.
Herein, it has been developed a method to prepare metallic foams starting from Zamak5 (ZnAlCu alloy) with different pore sizes. The Zamak5 metallic foam is designed to serve as a support and metallic precursor of ZIF-8. In this way, composite materials MOF-metal can be prepared, these composites have a large number of application in energy exchange processe such as: adsorption or chemical reactions. Additionally, this method of sythesizing MOFs is environmentally friendly thanks to absence of solvents. Hanerssing the low melting point of the linker, the linker is infiltrated into the foam where the foam and the linker react to form the ZIF-8. In this way we have managed to transform part of the foam into ZIF-8 crystals that remain adhered to the foam. The foams have been characterized and modeled studying the mechanical and electrical properties, finding that both can be predected by various models. Among these, Ashby and Mortensen models for mechanical properties and Ashby and Percolation model for electrical properties stand. Full article
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14 pages, 4235 KiB  
Article
A Cd(II) Luminescent Coordination Grid as a Multiresponsive Fluorescence Sensor for Cr(VI) Oxyanions and Cr(III), Fe(III), and Al(III) in Aqueous Medium
by Kuo-Shun Liao, Meng-Jung Tsai, Li-Jen Hsu, Chih-Min Wang and Jing-Yun Wu
Molecules 2021, 26(23), 7103; https://doi.org/10.3390/molecules26237103 - 24 Nov 2021
Cited by 2 | Viewed by 1334
Abstract
Hydro(solvo)thermal reactions of Cd(NO3)2, N-(pyridin-3-ylmethyl)-4-(pyridin-4-yl)-1,8-naphthalimide (NI-mbpy-34), and 5-bromobenzene-1,3-dicarboxylic acid (Br-1,3-H2bdc) afforded a luminescent coordination polymer, {[Cd(Br-1,3-bdc)(NI-mbpy-34)(H2O)]∙2H2O}n (1). Single-crystal X-ray diffraction analysis showed that 1 features a two-dimensional (2-D) gridlike [...] Read more.
Hydro(solvo)thermal reactions of Cd(NO3)2, N-(pyridin-3-ylmethyl)-4-(pyridin-4-yl)-1,8-naphthalimide (NI-mbpy-34), and 5-bromobenzene-1,3-dicarboxylic acid (Br-1,3-H2bdc) afforded a luminescent coordination polymer, {[Cd(Br-1,3-bdc)(NI-mbpy-34)(H2O)]∙2H2O}n (1). Single-crystal X-ray diffraction analysis showed that 1 features a two-dimensional (2-D) gridlike sql layer with the point symbol of (44·62), where the Cd(II) center adopts a {CdO5N2} pentagonal bipyramidal geometry. Thermogravimetric (TG) analysis confirmed the thermal stability of 1 up to about 340 °C, whereas XRPD patterns proved the maintenance of crystallinity and framework integrity of 1 in CH2Cl2, H2O, CH3OH, and toluene. Photoluminescence studies indicated that 1 displayed intense blue fluorescence emissions in both solid-state and H2O suspension-phase. Owing to the good fluorescent properties, 1 could serve as an excellent turn-off fluorescence sensor for selective and sensitive Cr(VI) detection in water, with LOD = 15.15 μM for CrO42 and 14.91 μM for Cr2O72, through energy competition absorption mechanism. In addition, 1 could also sensitively detect Cr3+, Fe3+, and Al3+ ions in aqueous medium via fluorescence-enhancement responses, with LOD = 2.81 μM for Cr3+, 3.82 μM for Fe3+, and 3.37 μM for Al3+, mainly through an absorbance-caused enhancement (ACE) mechanism. Full article
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19 pages, 4157 KiB  
Article
Statistically Optimum HKUST-1 Synthesized by Room Temperature Coordination Modulation Method for the Adsorption of Crystal Violet Dye
by Christian J. Wijaya, Suryadi Ismadji, Hakun W. Aparamarta and Setiyo Gunawan
Molecules 2021, 26(21), 6430; https://doi.org/10.3390/molecules26216430 - 25 Oct 2021
Cited by 10 | Viewed by 2545
Abstract
Due to its excellency and versatility, many synthesis methods and conditions were developed to produce HKUST-1 ([Cu3(BTC)2(H2O)3]n). However, the diversity of HKUST-1 was actually generated both in terms of characteristics and morphologies. Hence, [...] Read more.
Due to its excellency and versatility, many synthesis methods and conditions were developed to produce HKUST-1 ([Cu3(BTC)2(H2O)3]n). However, the diversity of HKUST-1 was actually generated both in terms of characteristics and morphologies. Hence, the consistency of HKUST-1 characteristics and morphologies needs to be maintained. The statistical analysis and optimization provide features to determine the best synthesis condition. Here, a room-temperature coordination modulation method was proposed to maintain the morphology of HKUST-1 while reducing energy consumption. In addition, response surface methodology (RSM) was used to demonstrate the statistical analysis and optimization of the synthesis of HKUST-1. The molar ratio of ligand to metal, reaction time, and acetic acid concentration were studied to determine their effects on HKUST-1. The optimum HKUST-1 was obtained by the synthesis with a molar ratio of ligand to metal of 0.4703 for 27.2 h using 5% v/v acetic acid concentration. The statistical analysis performed a good agreement with the experimental data and showed the significance of three desired parameters on HKUST-1. The optimum HKUST-1 had the adsorption capacity of 1005.22 mg/g with a removal efficiency of 92.31% towards CV dye. It could be reused up to 5 cycles with insignificant decrease in performance. Full article
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17 pages, 4117 KiB  
Article
PEEK–WC-Based Mixed Matrix Membranes Containing Polyimine Cages for Gas Separation
by Marcello Monteleone, Riccardo Mobili, Chiara Milanese, Elisa Esposito, Alessio Fuoco, Sonia La Cognata, Valeria Amendola and Johannes C. Jansen
Molecules 2021, 26(18), 5557; https://doi.org/10.3390/molecules26185557 - 13 Sep 2021
Cited by 8 | Viewed by 2692
Abstract
Membrane-based processes are taking a more and more prominent position in the search for sustainable and energy-efficient gas separation applications. It is known that the separation performance of pure polymers may significantly be improved by the dispersion of suitable filler materials in the [...] Read more.
Membrane-based processes are taking a more and more prominent position in the search for sustainable and energy-efficient gas separation applications. It is known that the separation performance of pure polymers may significantly be improved by the dispersion of suitable filler materials in the polymer matrix, to produce so-called mixed matrix membranes. In the present work, four different organic cages were dispersed in the poly(ether ether ketone) with cardo group, PEEK-WC. The m-xylyl imine and furanyl imine-based fillers yielded mechanically robust and selective films after silicone coating. Instead, poor dispersion of p-xylyl imine and diphenyl imine cages did not allow the formation of selective films. The H2, He, O2, N2, CH4, and CO2 pure gas permeability of the neat polymer and the MMMs were measured, and the effect of filler was compared with the maximum limits expected for infinitely permeable and impermeable fillers, according to the Maxwell model. Time lag measurements allowed the calculation of the diffusion coefficient and demonstrated that 20 wt % of furanyl imine cage strongly increased the diffusion coefficient of the bulkier gases and decreased the diffusion selectivity, whereas the m-xylyl imine cage slightly increased the diffusion coefficient and improved the size-selectivity. The performance and properties of the membranes were discussed in relation to their composition and morphology. Full article
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13 pages, 3045 KiB  
Article
A Nanoporous Supramolecular Metal–Organic Framework Based on a Nucleotide: Interplay of the π···π Interactions Directing Assembly and Geometric Matching of Aromatic Tails
by Rosaria Bruno, Teresa F. Mastropietro, Giovanni De Munno and Donatella Armentano
Molecules 2021, 26(15), 4594; https://doi.org/10.3390/molecules26154594 - 29 Jul 2021
Cited by 3 | Viewed by 1819
Abstract
Self-assembly is the most powerful force for creating ordered supramolecular architectures from simple components under mild conditions. π···π stacking interactions have been widely explored in modern supramolecular chemistry as an attractive reversible noncovalent tool for the nondestructive fabrication of materials for different applications. [...] Read more.
Self-assembly is the most powerful force for creating ordered supramolecular architectures from simple components under mild conditions. π···π stacking interactions have been widely explored in modern supramolecular chemistry as an attractive reversible noncovalent tool for the nondestructive fabrication of materials for different applications. Here, we report on the self-assembly of cytidine 5’-monophosphate (CMP) nucleotide and copper metal ions for the preparation of a rare nanoporous supramolecular metal-organic framework in water. π···π stacking interactions involving the aromatic groups of the ancillary 2,2’-bipyridine (bipy) ligands drive the self-assemblies of hexameric pseudo-amphiphilic [Cu6(bipy)6(CMP)2(µ-O)Br4]2+ units. Owing to the supramolecular geometric matching between the aromatic tails, a nanoporous crystalline phase with hydrophobic and hydrophilic chiral pores of 1.2 and 0.8 nanometers, respectively, was successfully synthesized. The encoded chiral information, contained on the enantiopure building blocks, is transferred to the final supramolecular structure, assembled in the very unusual topology 8T6. These kinds of materials, owing to chiral channels with chiral active sites from ribose moieties, where the enantioselective recognition can occur, are, in principle, good candidates to carry out efficient separation of enantiomers, better than traditional inorganic and organic porous materials. Full article
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9 pages, 22468 KiB  
Article
Photodegradation of Brilliant Green Dye by a Zinc bioMOF and Crystallographic Visualization of Resulting CO2
by Paula Escamilla, Marta Viciano-Chumillas, Rosaria Bruno, Donatella Armentano, Emilio Pardo and Jesús Ferrando-Soria
Molecules 2021, 26(13), 4098; https://doi.org/10.3390/molecules26134098 - 05 Jul 2021
Cited by 5 | Viewed by 2334
Abstract
We present a novel bio-friendly water-stable Zn-based MOF (1), derived from the natural amino acid L-serine, which was able to efficiently photodegrade water solutions of brilliant green dye in only 120 min. The total degradation was followed by UV-Vis spectroscopy [...] Read more.
We present a novel bio-friendly water-stable Zn-based MOF (1), derived from the natural amino acid L-serine, which was able to efficiently photodegrade water solutions of brilliant green dye in only 120 min. The total degradation was followed by UV-Vis spectroscopy and further confirmed by single-crystal X-ray crystallography, revealing the presence of CO2 within its channels. Reusability studies further demonstrate the structural and performance robustness of 1. Full article
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11 pages, 2363 KiB  
Article
Metal Organic Frameworks Derived Fe-N-C Nanostructures as High-Performance Electrodes for Sodium Ion Batteries and Electromagnetic Interference (EMI) Shielding
by Vadahanambi Sridhar, Inwon Lee and Hyun Park
Molecules 2021, 26(4), 1018; https://doi.org/10.3390/molecules26041018 - 15 Feb 2021
Cited by 9 | Viewed by 2595
Abstract
Metal organic framework (MOF)-derived carbon nanostructures (MDC) synthesized by either calcinations or carbonization or pyrolysis are emerging as attractive materials for a wide range of applications like batteries, super-capacitors, sensors, water treatment, etc. But the process of transformation of MOFs into MDCs is [...] Read more.
Metal organic framework (MOF)-derived carbon nanostructures (MDC) synthesized by either calcinations or carbonization or pyrolysis are emerging as attractive materials for a wide range of applications like batteries, super-capacitors, sensors, water treatment, etc. But the process of transformation of MOFs into MDCs is time-consuming, with reactions requiring inert atmospheres and reaction time typically running into hours. In this manuscript, we report the transformation of 1,4-diazabicyclo[2.2.2]octane, (DABCO)-based MOFs into iron nitride nanoparticles embedded in nitrogen-doped carbon nanotubes by simple, fast and facile microwave pyrolysis. By using graphene oxide and carbon fiber as microwave susceptible surfaces, three-dimensional nitrogen-doped carbon nanotubes vertically grown on reduced graphene oxide (MDNCNT@rGO) and carbon fibers (MDCNT@CF), respectively, were obtained, whose utility as anode material in sodium-ion batteries (MDNCNT@rGO) and for EMI (electromagnetic interference) shielding material (MDCNT@CF) is reported. Full article
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19 pages, 17619 KiB  
Article
Design of Metal-Organic Framework Templated Materials Using High-Throughput Computational Screening
by Momin Ahmad, Yi Luo, Christof Wöll, Manuel Tsotsalas and Alexander Schug
Molecules 2020, 25(21), 4875; https://doi.org/10.3390/molecules25214875 - 22 Oct 2020
Cited by 11 | Viewed by 5645
Abstract
The ability to crosslink Metal-Organic Frameworks (MOFs) has recently been discovered as a flexible approach towards synthesizing MOF-templated “ideal network polymers”. Crosslinking MOFs with rigid cross-linkers would allow the synthesis of crystalline Covalent-Organic Frameworks (COFs) of so far unprecedented flexibility in network topologies, [...] Read more.
The ability to crosslink Metal-Organic Frameworks (MOFs) has recently been discovered as a flexible approach towards synthesizing MOF-templated “ideal network polymers”. Crosslinking MOFs with rigid cross-linkers would allow the synthesis of crystalline Covalent-Organic Frameworks (COFs) of so far unprecedented flexibility in network topologies, far exceeding the conventional direct COF synthesis approach. However, to date only flexible cross-linkers were used in the MOF crosslinking approach, since a rigid cross-linker would require an ideal fit between the MOF structure and the cross-linker, which is experimentally extremely challenging, making in silico design mandatory. Here, we present an effective geometric method to find an ideal MOF cross-linker pair by employing a high-throughput screening approach. The algorithm considers distances, angles, and arbitrary rotations to optimally match the cross-linker inside the MOF structures. In a second, independent step, using Molecular Dynamics (MD) simulations we quantitatively confirmed all matches provided by the screening. Our approach thus provides a robust and powerful method to identify ideal MOF/Cross-linker combinations, which helped to identify several MOF-to-COF candidate structures by starting from suitable libraries. The algorithms presented here can be extended to other advanced network structures, such as mechanically interlocked materials or molecular weaving and knots. Full article
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Review

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33 pages, 9979 KiB  
Review
Present and Perspectives of Photoactive Porous Composites Based on Semiconductor Nanocrystals and Metal-Organic Frameworks
by Alejandro Cortés-Villena and Raquel E. Galian
Molecules 2021, 26(18), 5620; https://doi.org/10.3390/molecules26185620 - 16 Sep 2021
Cited by 6 | Viewed by 3598
Abstract
This review focuses on the recent developments in synthesis, properties, and applications of a relatively new family of photoactive porous composites, integrated by metal halide perovskite (MHP) nanocrystals and metal-organic frameworks (MOFs). The synergy between the two systems has led to materials (MHP@MOF [...] Read more.
This review focuses on the recent developments in synthesis, properties, and applications of a relatively new family of photoactive porous composites, integrated by metal halide perovskite (MHP) nanocrystals and metal-organic frameworks (MOFs). The synergy between the two systems has led to materials (MHP@MOF composites) with new functionalities along with improved properties and phase stability, thus broadening their applications in multiple areas of research such as sensing, light-harvesting solar cells, light-emitting device technology, encryption, and photocatalysis. The state of the art, recent progress, and most promising routes for future research on these photoactive porous composites are presented in the end. Full article
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