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Emerging Applications of Metal-Organic Frameworks and Related Porous Materials

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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 34285

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Special Issue Editors

Prof. Dr. Emilio Pardo

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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

Dr. Jesús Ferrando Soria

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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

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Keywords

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

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Published Papers (10 papers)

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Research

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18 pages, 7106 KiB

Open AccessFeature PaperArticle

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 7 | Viewed by 2843

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 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

(This article belongs to the Special Issue Emerging Applications of Metal-Organic Frameworks and Related Porous Materials)

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12 pages, 6142 KiB

Open AccessArticle

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 16 | Viewed by 2760

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 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

(This article belongs to the Special Issue Emerging Applications of Metal-Organic Frameworks and Related Porous Materials)

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14 pages, 4235 KiB

Open AccessArticle

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 1713

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 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

(This article belongs to the Special Issue Emerging Applications of Metal-Organic Frameworks and Related Porous Materials)

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19 pages, 4157 KiB

Open AccessArticle

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 11 | Viewed by 3484

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, 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

(This article belongs to the Special Issue Emerging Applications of Metal-Organic Frameworks and Related Porous Materials)

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17 pages, 4117 KiB

Open AccessArticle

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 13 | Viewed by 3279

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 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

(This article belongs to the Special Issue Emerging Applications of Metal-Organic Frameworks and Related Porous Materials)

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13 pages, 3045 KiB

Open AccessArticle

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 2226

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. 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

(This article belongs to the Special Issue Emerging Applications of Metal-Organic Frameworks and Related Porous Materials)

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9 pages, 22468 KiB

Open AccessFeature PaperArticle

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 - 5 Jul 2021

Cited by 7 | Viewed by 2793

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 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

(This article belongs to the Special Issue Emerging Applications of Metal-Organic Frameworks and Related Porous Materials)

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11 pages, 2363 KiB

Open AccessArticle

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 10 | Viewed by 3034

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 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

(This article belongs to the Special Issue Emerging Applications of Metal-Organic Frameworks and Related Porous Materials)

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19 pages, 17619 KiB

Open AccessArticle

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 12 | Viewed by 6588

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, 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

(This article belongs to the Special Issue Emerging Applications of Metal-Organic Frameworks and Related Porous Materials)

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33 pages, 9979 KiB

Open AccessReview

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 8 | Viewed by 4314

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 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

(This article belongs to the Special Issue Emerging Applications of Metal-Organic Frameworks and Related Porous Materials)

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