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Metal Organic Frameworks: Synthesis and Application II

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

Deadline for manuscript submissions: closed (31 January 2024) | Viewed by 16868

Special Issue Editors


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Guest Editor
Laboratory of Analytical Chemistry, School of Chemistry, Aristotle University of Thessaloniki, 54124 Thessaloniki, Greece
Interests: analytical chemistry; sample preparation; chromatography; HPLC; method validation; method development; separation science; food analysis; bioanalysis; environmental analysis; green analytical chemistry; sorptive extraction; microextraction techniques
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Guest Editor
Chemistry Department, Aristotle University of Thessaloniki, GR54124 Thessaloniki, Greece
Interests: materials chemistry; materials characterization; nanomaterials; graphene oxide; activated carbon; wastewater treatment; separation; adsorption; catalytic oxidation; environmental applications
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Following a very successful first run, we are pleased to announce the launch of a second edition of a Special Issue on the synthesis and application of metal–organic frameworks, instigated by the still wide applicability of MOFs in analytical science as materials with exceptional properties and advantages. As such, we are inviting authors to present their experience with regard to MOFs’ use.

Metal–organic frameworks (MOFs) are among the most promising novel materials. They belong to a new class of crystalline materials that consist of a coordination bond between metal clusters (e.g., metal–carboxylate clusters and metal–azolate clusters), metal atoms, or rod-shaped clusters and multidentate organic linkers that contain oxygen or nitrogen donors (carboxylates, azoles, nitriles, etc.), thus forming a three-dimensional structure.

The properties of both metal ions and linkers determine the physical properties of MOF networks (e.g., porosity, pore size, and pore surface). Additionally, the structural properties of the prepared frameworks can be controlled by the solvent system, pH, metal–ligand ratio, and temperature.

The concept of MOFs was first introduced in 1990. They were initially used in catalysis, gas separation, membranes, and electrochemical sensors. Later on, they were introduced as SPE (solid phase extraction) sorbents for PAHs (polycyclic aromatic hydrocarbons) in environmental water samples, then the range expanded to the field of analytical chemistry, both in chromatographic separation and sample preparation, with great success in, e.g., SPE and SPME (solid phase mico-extraction). Since then, the number of analytical applications implementing MOFs as sorbents in sorptive sample preparation approaches has been steadily increasing. Τhis is reinforced by the fact that, at least theoretically, an infinite number of structures can be designed and synthesized, thus making tuneability one of the most unique characteristics of MOF materials. Moreover, they have been designed in various shapes, such as columns, fibers, and films, so that they can meet more analytical challenges with improved analytical features.

Their exceptional properties have attracted the interest of analytical chemists who have taken advantage of their unique structures and properties and have already introduced them in several sample pretreatment techniques, such as solid phase extraction, dispersive SPE, magnetic solid phase extraction, solid phase microextraction, stir bar sorptive extraction, etc.

This Special Issue aims to present recent developmentts in the synthesis and applications of MOFs.

Prof. Dr. Victoria Samanidou
Prof. Dr. Eleni Deliyanni
Guest Editors

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Keywords

  • Metal–organic framework
  • Catalysis 
  • Sample preparation
  • Sensors
  • Gas extraction
  • Sorptive extraction

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Published Papers (9 papers)

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Research

16 pages, 4756 KiB  
Article
Adsorptive Elimination of a Cationic Dye and a Hg (II)-Containing Antiseptic from Simulated Wastewater Using a Metal Organic Framework
by Nilanjan Roy, Chanchal Das, Mohuya Paul, Jungkyun Im and Goutam Biswas
Molecules 2024, 29(4), 886; https://doi.org/10.3390/molecules29040886 - 17 Feb 2024
Viewed by 680
Abstract
Several types of pollutants have acute adverse effects on living bodies, and the effective removal of these pollutants remains a challenge. Safranin O (a biological dye) and merbromin (a topical mercury-containing antiseptic) are considered organic pollutants, and there are only a few reports [...] Read more.
Several types of pollutants have acute adverse effects on living bodies, and the effective removal of these pollutants remains a challenge. Safranin O (a biological dye) and merbromin (a topical mercury-containing antiseptic) are considered organic pollutants, and there are only a few reports on their removal. Synthesized and well-characterized (through PXRD, FTIR, FESEM, and EDS analysis) MOF-5 was used for the first time in the removal of safranin O and merbromin from simulated wastewater and real wastewater. In both cases, MOF-5 effectively removed contaminants. We found that in simulated wastewater, the highest efficiency of removal of safranin O was 53.27% (for 15 mg/L) at pH 10, and for merbromin, it was 41.49% (for 25 mg/L) at pH 6. In the case of real wastewater containing natural ions (Na+, K+, F, Cl, SO42−, PO43−, Mg2+, and Ca2+) and other molecules, the removal efficiencies of these two dyes decreased (34.00% and 26.28% for safranin O and merbromin, respectively) because of the presence of other ions and molecules. A plausible mechanism for the removal of these pollutants using MOF-5 was proposed. Full article
(This article belongs to the Special Issue Metal Organic Frameworks: Synthesis and Application II)
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14 pages, 3604 KiB  
Article
Green Ultrasound-Assisted Synthesis of Rare-Earth-Based MOFs
by Francesca Lo Presti, Anna L. Pellegrino, Nancy Consoli and Graziella Malandrino
Molecules 2023, 28(16), 6088; https://doi.org/10.3390/molecules28166088 - 16 Aug 2023
Cited by 2 | Viewed by 1596
Abstract
Rare-earth (RE)-based metal organic frameworks (MOFs) are quickly gaining popularity as flexible functional materials in a variety of technological fields. These MOFs are useful for more than just conventional uses like gas sensors and catalyst materials; in fact, they also show significant promise [...] Read more.
Rare-earth (RE)-based metal organic frameworks (MOFs) are quickly gaining popularity as flexible functional materials in a variety of technological fields. These MOFs are useful for more than just conventional uses like gas sensors and catalyst materials; in fact, they also show significant promise in emerging technologies including photovoltaics, optical, and biomedical applications. Using yttrium and europium as ionic host centres and dopants, respectively, and 1,3,5-benzenetricarboxylic acid (H3-BTC) as an organic linker, we describe a simple and green approach for the fabrication of RE-MOFs. Specifically, Y-BTCs and Eu-doped Y-BTCs MOFs have been synthesised in a single step using an eco-friendly method that makes use of ultrasound technology. To establish a correlation between the morphological and structural properties and reaction conditions, a range of distinct reaction periods has been employed for the synthetic processes. Detailed analyses of the synthesised samples through powder X-ray diffraction (PXRD), field emission scanning electron microscopy (FE-SEM), and Fourier-transform infrared spectroscopy (FT-IR) have confirmed the phase formation. Furthermore, thermal analyses such as thermogravimetric analysis (TGA) have been employed to evaluate the thermal stability and structural modifications of the Y-BTC and Eu-doped Y-BTC samples. Finally, the luminescent properties of the synthesised samples doped with Eu3+ have been assessed, providing an evaluation of their characteristics. As a proof of concept, an Eu-doped Y-BTC sample has been applied for the sensing of nitrobenzene as a molecule test of nitro derivatives. Full article
(This article belongs to the Special Issue Metal Organic Frameworks: Synthesis and Application II)
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17 pages, 3553 KiB  
Article
Anchoring of Polymer Loops on Enzyme-Immobilized Mesoporous ZIF-8 Enhances the Recognition Selectivity of Angiotensin-Converting Enzyme Inhibitory Peptides
by Zefen Wang, Qian Zhou, Siyuan Liu, Dankui Liao, Pengru Liu and Xiongdiao Lan
Molecules 2023, 28(7), 3117; https://doi.org/10.3390/molecules28073117 - 31 Mar 2023
Viewed by 1388
Abstract
Immobilized angiotensin-converting enzyme (ACE) is a promising material for the rapid screening of antihypertensive drugs, but the nonspecific adsorption is a serious problem in separation processes involving complex biological products. In this study, triblock copolymers with dopamine (DA) block as anchors and PEG [...] Read more.
Immobilized angiotensin-converting enzyme (ACE) is a promising material for the rapid screening of antihypertensive drugs, but the nonspecific adsorption is a serious problem in separation processes involving complex biological products. In this study, triblock copolymers with dopamine (DA) block as anchors and PEG block as the main body (DA-PEGx-DA) were attached to an immobilized ACE (ACE@mZIF-8/PDA, AmZP) surface via the “grafting to” strategy which endowed them with anti-nonspecific adsorption. The influence of DA-PEGx-DA chain length on nonspecific adsorption was confirmed. The excellent specificity and reusability of the obtained ACE@mZIF-8/PDA/DA-PEG5000-DA (AmZPP5000) was validated by screening two known ACE inhibitory peptides Val-Pro-Pro (VPP, competitive inhibitory peptides of ACE) and Gly-Met-Lys-Cys-Ala-Phe (GF-6, noncompetitive inhibitory peptides of ACE) from a mixture containing active and inactive compounds. These results demonstrate that anchored polymer loops are effective for high-recognition selectivity and AmZPP5000 is a promising compound for the efficient separation of ACE inhibitors in biological samples. Full article
(This article belongs to the Special Issue Metal Organic Frameworks: Synthesis and Application II)
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19 pages, 16199 KiB  
Article
Metal and Ligand Effect on the Structural Diversity of Divalent Coordination Polymers with Mixed Ligands: Evaluation for Photodegradation
by Manivannan Govindaraj, Shih-Ying Zhong, Chia-Her Lin and Jhy-Der Chen
Molecules 2023, 28(5), 2226; https://doi.org/10.3390/molecules28052226 - 27 Feb 2023
Cited by 3 | Viewed by 1081
Abstract
Eight coordination polymers constructed from divalent metal salts, N,N-bis(pyridin-3-ylmethyl)terephthalamide (L), and various dicarboxylic acids are reported, affording [Co(L)(5-ter-IPA)(H2O)2]n (5-tert-H2IPA = 5-tert-butylisophthalic acid), 1, {[Co(L)(5-NO2-IPA)]⋅2H2 [...] Read more.
Eight coordination polymers constructed from divalent metal salts, N,N-bis(pyridin-3-ylmethyl)terephthalamide (L), and various dicarboxylic acids are reported, affording [Co(L)(5-ter-IPA)(H2O)2]n (5-tert-H2IPA = 5-tert-butylisophthalic acid), 1, {[Co(L)(5-NO2-IPA)]⋅2H2O}n (5-NO2-H2IPA = 5-nitroisophthalic acid), 2, {[Co(L)0.5(5-NH2-IPA)]⋅MeOH}n (5-NH2-H2IPA = 5-aminoisophthalic acid), 3, {[Co(L)(MBA)]⋅2H2O}n (H2MBA = diphenylmethane-4,4′–dicarboxylic acid), 4, {[Co(L)(SDA)]⋅H2O}n (H2SDA = 4,4-sulfonyldibenzoic acid), 5, {[Co2(L)2(1,4-NDC)2(H2O)2]⋅5H2O}n (1,4-H2NDC = naphthalene-1,4-dicarboxylic acid), 6, {[Cd(L)(1,4-NDC)(H2O)]⋅2H2O}n, 7, and {[Zn2(L)2(1,4-NDC)2]⋅2H2O}n, 8, which were structurally characterized by using single-crystal X-ray diffraction. The structural types of 18 are subject to the metal and ligand identities, showing a 2D layer with the hcb, a 3D framework with the pcu, a 2D layer with the sql, a polycatenation of 2-fold interpenetrated 2D layer with the sql, a 2-fold interpenetrated 2D layer with the 2,6L1, a 3D framework with the cds, a 2D layer with the 2,4L1, and a 2D layer with the (102⋅12)(10)2(4⋅10⋅124)(4) topologies, respectively. The investigation on the photodegradation of methylene blue (MB) by using complexes 13 reveals that the degradation efficiency may increase with increasing surface areas. Full article
(This article belongs to the Special Issue Metal Organic Frameworks: Synthesis and Application II)
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16 pages, 5303 KiB  
Article
Composite Materials Based on a Zr4+ MOF and Aluminosilicates for the Simultaneous Removal of Cationic and Anionic Dyes from Aqueous Media
by Petros Georgianos, Anastasia D. Pournara, Evangelos K. Andreou, Gerasimos S. Armatas and Manolis J. Manos
Molecules 2023, 28(2), 815; https://doi.org/10.3390/molecules28020815 - 13 Jan 2023
Cited by 4 | Viewed by 1718
Abstract
Environmental pollution has been a reality for many decades, with its contamination intensifying daily due to rapid urbanization and the ever-increasing world population. Dyes, and especially synthetic ones, constitute a category of pollutants that not only affect the quality of water but also [...] Read more.
Environmental pollution has been a reality for many decades, with its contamination intensifying daily due to rapid urbanization and the ever-increasing world population. Dyes, and especially synthetic ones, constitute a category of pollutants that not only affect the quality of water but also exhibit high toxicity toward living organisms. This study was thoroughly planned to explore the removal of two toxic dyes, namely the methylene blue (MB) and methyl orange (MO) compounds from contaminated aqueous media. For this purpose, we designed and synthesized two new composite materials based on ammonium-functionalized Zr4+ MOF (MOR-1 or UiO-66-NH3+) and naturally occurring sorbents, such as bentonite and clinoptilolite. The composite materials displayed exceptional sorption capability toward both MB+ and MO ions. A key finding of this study was the high efficiency of the composite materials to simultaneously remove MB+ and MO under continuous flow conditions, also showing regeneration capability and reusability, thus providing an alternative to well-known mixed bed resins. Full article
(This article belongs to the Special Issue Metal Organic Frameworks: Synthesis and Application II)
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13 pages, 2947 KiB  
Article
In Situ Electrospun Porous MIL-88A/PAN Nanofibrous Membranes for Efficient Removal of Organic Dyes
by Hao Wu, Le Xu, Jiao Jia, Fengchun Dong, Yongtang Jia and Xi Liu
Molecules 2023, 28(2), 760; https://doi.org/10.3390/molecules28020760 - 12 Jan 2023
Cited by 7 | Viewed by 1994
Abstract
In recent years, metal–organic framework (MOF)-based nanofibrous membranes (NFMs) have received extensive attention in the application of water treatment. Hence, it is of great significance to realize a simple and efficient preparation strategy of MOF-based porous NFMs. Herein, we developed a direct in [...] Read more.
In recent years, metal–organic framework (MOF)-based nanofibrous membranes (NFMs) have received extensive attention in the application of water treatment. Hence, it is of great significance to realize a simple and efficient preparation strategy of MOF-based porous NFMs. Herein, we developed a direct in situ formation of MOF/polymer NFMs using an electrospinning method. The porous MOF/polymer NFMs were constructed by interconnecting mesopores in electrospun composite nanofibers using poly(vinylpolypyrrolidone) (PVP) as the sacrificial pore-forming agent. MOF (MIL-88A) particles were formed inside the polyacrylonitrile (PAN)/PVP nanofibers in situ during electrospinning, and the porous MIL-88A/PAN (pMIL-88A/PAN) NFM was obtained after removing PVP by ethanol and water washing. The MOF particles were uniformly distributed throughout the pMIL-88A/PAN NFM, showing a good porous micro-nano morphological structure of the NFM with a surface area of 143.21 m2 g−1, which is conducive to its efficient application in dye adsorption and removal. Specifically, the dye removal efficiencies of the pMIL-88A/PAN NFM for amaranth red, rhodamine B, and acid blue were as high as 99.2, 94.4, and 99.8%, respectively. In addition, the NFM still showed over 80% dye removal efficiencies after five adsorption cycles. The pMIL-88A/PAN NFM also presented high adsorption capacities, fast adsorption kinetics, and high cycling stabilities during the processes of dye adsorption and removal. Overall, this work demonstrates that the in situ electrospun porous MOF/polymer NFMs present promising application potential in water treatment for organic dyestuff removal. Full article
(This article belongs to the Special Issue Metal Organic Frameworks: Synthesis and Application II)
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13 pages, 4832 KiB  
Article
Valorization of CO2 through the Synthesis of Cyclic Carbonates Catalyzed by ZIFs
by José J. Delgado-Marín, Iris Martín-García, David Villalgordo-Hernández, Francisco Alonso, Enrique V. Ramos-Fernández and Javier Narciso
Molecules 2022, 27(22), 7791; https://doi.org/10.3390/molecules27227791 - 12 Nov 2022
Cited by 8 | Viewed by 1948
Abstract
One way to exploit CO2 is to use it as a feedstock for the production of cyclic carbonates via its reaction with organic epoxides. As far as we know, there is still no heterogeneous catalyst that accelerates the reaction in a selective, [...] Read more.
One way to exploit CO2 is to use it as a feedstock for the production of cyclic carbonates via its reaction with organic epoxides. As far as we know, there is still no heterogeneous catalyst that accelerates the reaction in a selective, efficient and industrially usable way. Cobalt and zinc-based zeolitic imidazole frameworks (ZIFs) have been explored as heterogeneous catalysts for this reaction. In particular, we have prepared ZIF-8 and ZIF-67 catalysts, which have been modified by partial replacement of 2-methylimidazole by 1,2,4-triazole, in order to introduce uncoordinated nitrogen groups with the metal. The catalysts have shown very good catalytic performance, within the best of the heterogeneous catalysts tested in the cycloaddition of CO2 with epichlorohydrin. The catalytic activity is due ultimately to defects on the outer surface of the crystal, and varies in the order of ZIF-67-m > ZIF-67 > ZiF-8-m = ZIF-8. Notably, reactions take place under mild reaction conditions and without the use of co-catalysts. Full article
(This article belongs to the Special Issue Metal Organic Frameworks: Synthesis and Application II)
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19 pages, 6853 KiB  
Article
Biological Effects of EGCG@MOF Zn(BTC)4 System Improves Wound Healing in Diabetes
by Song Li, Jing Yan, Qiangqiang Zhu, Xinxiang Liu, Senlin Li, Shenhou Wang, Xuanjun Wang and Jun Sheng
Molecules 2022, 27(17), 5427; https://doi.org/10.3390/molecules27175427 - 25 Aug 2022
Cited by 10 | Viewed by 2112
Abstract
Tea contains high levels of the compound epigallocatechin gallate (EGCG). It is considered an important functional component in tea and has anti-cancer, antioxidant, and anti-inflammatory effects. The eight phenolic hydroxyl groups in EGCG’s chemical structure are the basis for EGCG’s multiple biological effects. [...] Read more.
Tea contains high levels of the compound epigallocatechin gallate (EGCG). It is considered an important functional component in tea and has anti-cancer, antioxidant, and anti-inflammatory effects. The eight phenolic hydroxyl groups in EGCG’s chemical structure are the basis for EGCG’s multiple biological effects. At the same time, it also leads to poor chemical stability, rendering EGCG prone to oxidation and isomerization reactions that change its original structure and biological activity. Learning how to maintain the activity of EGCG has become an important goal in understanding the biological activity of EGCG and the research and development of tea-related products. Metal–organic frameworks (MOFs) are porous materials with a three-dimensional network structure that are composed of inorganic metals or metal clusters together with organic complexes. MOFs exploit the porous nature of the material itself. When a drug is an appropriate size, it can be wrapped into the pores by physical or chemical methods; this allows the drug to be released slowly, and MOFs can also reduce drug toxicity. In this study, we used MOF Zn(BTC)4 materials to load EGCG and investigated the sustained release effect of EGCG@MOF Zn(BTC)4 and the biological effects on wound healing in a diabetic mouse model. Full article
(This article belongs to the Special Issue Metal Organic Frameworks: Synthesis and Application II)
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20 pages, 4402 KiB  
Article
Cooling Capacity Test for MIL-101(Cr)/CaCl2 for Adsorption Refrigeration System
by Zhongbao Liu, Banghua Zhao, Yong Huang, Xin Qi and Fengfei Lou
Molecules 2020, 25(17), 3975; https://doi.org/10.3390/molecules25173975 - 31 Aug 2020
Cited by 13 | Viewed by 3027
Abstract
An MIL-101(Cr) powder material was successfully prepared using the hydrothermal synthesis method, and then the original MIL-101(Cr) was combined with different mass fractions of CaCl2 using the immersion method to obtain a MIL-101(Cr)/CaCl2 composite material. The physical properties of the adsorbent [...] Read more.
An MIL-101(Cr) powder material was successfully prepared using the hydrothermal synthesis method, and then the original MIL-101(Cr) was combined with different mass fractions of CaCl2 using the immersion method to obtain a MIL-101(Cr)/CaCl2 composite material. The physical properties of the adsorbent were determined by X-ray powder diffraction (XRD), an N2 adsorption desorption isotherm test, and thermogravimetric analysis (TG). The water vapor adsorption performance of the metal-organic frameworks MOFs was tested with a gravimetric water vapor adsorption instrument to analyze its water vapor adsorption mechanism. Based on the SIMULINK platform in the MATLAB software, a simulation model of the coefficient of performance (COP) and cooling capacity of the adsorption refrigeration system was established, and the variation trends of the COP and cooling capacity of the adsorption refrigeration system under different evaporation/condensation/adsorption/desorption temperatures was theoretically studied. MIL101-(Cr)/CaCl2-20% was selected as the adsorption material in the adsorption refrigeration system through the physical characterization of composite materials with different CaCl2 concentrations by means of adsorption water vapor test experiments. A closed adsorption system performance test device was built based on the liquid level method. The cooling power per unit and adsorbent mass (COP and SCP) of the system were tested at different evaporation temperatures (288 K/293 K/298 K); the adsorption temperature was 298 K, the condensation temperature was 308 K, and the desorption temperature was 353 K. The experimental results showed that COP and SCP increased with the increase in the evaporation temperature. When the evaporation temperature was 298 K, the level of COP was 0.172, and the level of SCP was 136.9 W/kg. The COP and SCP of the system were tested at different adsorption temperatures (293 K/298 K/303 K); the evaporation temperature was 288 K, the condensation temperature was 308 K, and the desorption temperature was 353 K. The experimental results showed that the levels of COP and SCP decreased with the increase in the adsorption temperature. When the adsorption temperature was 293 K, the level of COP was 0.18, and the level of SCP was 142.4 W/kg. Full article
(This article belongs to the Special Issue Metal Organic Frameworks: Synthesis and Application II)
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