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Metal Organic Frameworks: Synthesis and Application

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A special issue of Molecules (ISSN 1420-3049).

Deadline for manuscript submissions: closed (15 September 2019) | Viewed by 77418

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Prof. Dr. Victoria Samanidou

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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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Prof. Dr. Eleni Deliyanni

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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
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Dear Colleagues,

Metal–organic frameworks (MOFs) are among the most promising novel materials. These belong to a new class of crystalline materials that consist of 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 (like carboxylates, azoles, nitriles, etc.), thus, a three-dimensional structure is formed.

The properties of both metal ions and linkers determine the physical properties of MOFs 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 actually initially used in catalysis, gas separation, membranes, 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 is 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 attracted the interest of analytical chemists who have taken advantage of the 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 the recent developmentts in the synthesis and applications of MOFs.

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

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Keywords

metal organic framework
catalysis
sample preparation
sensors
gas extraction
sorptive extraction

Related Special Issue

Metal Organic Frameworks: Synthesis and Application II in Molecules (9 articles)

Published Papers (11 papers)

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Editorial

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3 pages, 182 KiB

Open AccessEditorial

Metal Organic Frameworks: Synthesis and Application

by Victoria F. Samanidou and Eleni A. Deliyanni

Molecules 2020, 25(4), 960; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25040960 - 20 Feb 2020

Cited by 17 | Viewed by 4407

Abstract

The concept of metal–organic frameworks (MOFs) was first introduced in 1990; nowadays they are among the most promising novel materials [...] Full article

(This article belongs to the Special Issue Metal Organic Frameworks: Synthesis and Application)

Research

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8 pages, 1220 KiB

Open AccessFeature PaperCommunication

Hydrogen-Bonding Linkers Yield a Large-Pore, Non-Catenated, Metal-Organic Framework with pcu Topology

by Mohammad S. Yazdanparast, Victor W. Day and Tendai Gadzikwa

Molecules 2020, 25(3), 697; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25030697 - 06 Feb 2020

Cited by 8 | Viewed by 4001

Abstract

Pillared paddle-wheel-based metal-organic framework (MOF) materials are an attractive target as they offer a reliable method for constructing well-defined, multifunctional materials. A drawback of these materials, which has limited their application, is their tendency to form catenated frameworks with little accessible volume. To eliminate this disadvantage, it is necessary to investigate strategies for constructing non-catenated pillared paddle-wheel MOFs. Hydrogen-bonding substituents on linkers have been postulated to prevent catenation in certain frameworks and, in this work, we present a new MOF to further bolster this theory. Using 2,2′-diamino-[1,1′-biphenyl]-4,4′-dicarboxylic acid, BPDC-(NH₂)₂, linkers and dipyridyl glycol, DPG, pillars, we assembled a MOF with pcu topology. The new material is non-catenated, exhibiting large accessible pores and low density. To the best of our knowledge, this material constitutes the pcu framework with the largest pore volume and lowest density. We attribute the lack of catenation to the presence of H-bonding substituents on both linkers. Full article

(This article belongs to the Special Issue Metal Organic Frameworks: Synthesis and Application)

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14 pages, 3417 KiB

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Dual Emission in a Ligand and Metal Co-Doped Lanthanide-Organic Framework: Color Tuning and Temperature Dependent Luminescence

by Despoina Andriotou, Stavros A. Diamantis, Anna Zacharia, Grigorios Itskos, Nikos Panagiotou, Anastasios J. Tasiopoulos and Theodore Lazarides

Molecules 2020, 25(3), 523; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25030523 - 25 Jan 2020

Cited by 7 | Viewed by 3493

Abstract

In this study, we report the luminescence color tuning in the lanthanide metal-organic framework (LnMOF) ([La(bpdc)Cl(DMF)] (1); bpdc²⁻ = [1,1′-biphenyl]-4,4′-dicarboxylate, DMF = N,N-dimethylformamide) by introducing dual emission properties in a La³⁺ MOF scaffold through doping with the blue fluorescent 2,2′-diamino-[1,1′-biphenyl]-4,4′-dicarboxylate (dabpdc²⁻) and the red emissive Eu³⁺. With a careful adjustment of the relative doping levels of the lanthanide ions and bridging ligands, the color of the luminescence was modulated, while at the same time the photophysical characteristics of the two chromophores were retained. In addition, the photophysical properties of the parent MOF (1) and its doped counterparts with various dabpdc²⁻/bpdc²⁻ and Eu³⁺/La³⁺ ratios and the photoinduced energy transfer pathways that are possible within these materials are discussed. Finally, the temperature dependence study on the emission profile of a doped analogue containing 10% dabpdc²⁻ and 2.5% Eu³⁺ (7) is presented, highlighting the potential of this family of materials to behave as temperature sensors. Full article

(This article belongs to the Special Issue Metal Organic Frameworks: Synthesis and Application)

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14 pages, 4695 KiB

Open AccessFeature PaperArticle

Building MOF Nanocomposites with Oxidized Graphitic Carbon Nitride Nanospheres: The Effect of Framework Geometry on the Structural Heterogeneity

by Dimitrios A. Giannakoudakis and Teresa J. Bandosz

Molecules 2019, 24(24), 4529; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules24244529 - 11 Dec 2019

Cited by 14 | Viewed by 3950

Abstract

Composite of two MOFs, copper-based Cu-BTC (HKUST-1) and zirconium-based Zr-BDC (UiO-66), with oxidized graphitic carbon nitride nanospheres were synthesized. For comparison, pure MOFs were also obtained. The surface features were analyzed using x-ray diffraction (XRD), sorption of nitrogen, thermal analysis, and scanning electron microscopy (SEM). The incorporation of oxidized g-C₃N₄ to the Cu-BTC framework caused the formation of a heterogeneous material of a hierarchical pores structure, but a decreased surface area when compared to that of the parent MOF. In the case of UiO-66, functionalized nanospheres were acting as seeds around which the crystals grew. Even though the MOF phases were detected in both materials, the porosity analysis indicated that in the case of Cu-BTC, a collapsed MOF/nonporous and amorphous matter was also present and the MOF phase was more defectous than that in the case of UiO-66. The results suggested different roles of oxidized g-C₃N₄ during the composite synthesis, depending on the MOF geometry. While spherical units of UiO-66 grew undisturbed around oxidized and spherical g-C₃N₄, octahedral Cu-BTC units experienced geometrical constraints, leading to more defects, a disturbed growth of the MOF phase, and to the formation of mesopores at the contacts between the spheres and MOF units. The differences in the amounts of CO₂ adsorbed between the MOFs and the composites confirm the proposed role of oxidized g-C₃N₄ in the composite formation. Full article

(This article belongs to the Special Issue Metal Organic Frameworks: Synthesis and Application)

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14 pages, 3685 KiB

Open AccessFeature PaperArticle

Mixed Functionalization of Organic Ligands in UiO-66: A Tool to Design Metal–Organic Frameworks for Tailored Microextraction

by Gabriel González-Rodríguez, Iván Taima-Mancera, Ana B. Lago, Juan H. Ayala, Jorge Pasán and Verónica Pino

Molecules 2019, 24(20), 3656; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules24203656 - 10 Oct 2019

Cited by 14 | Viewed by 3937

Abstract

The mixed-ligand strategy was selected as an approach to tailor a metal–organic framework (MOF) with microextraction purposes. The strategy led to the synthesis of up to twelve UiO-66-based MOFs with different amounts of functionalized terephthalate ligands (H-bdc), including nitro (-NO₂) and amino (-NH₂) groups (NO₂-bdc and NH₂-bdc, respectively). Increases of 25% in ligands were used in each case, and different pore environments were thus obtained in the resulting crystals. Characterization of MOFs includes powder X-ray diffraction, infrared spectroscopy, and elemental analysis. The obtained MOFs with different degrees and natures of functionalization were tested as sorbents in a dispersive miniaturized solid-phase extraction (D-µSPE) method in combination with high-performance liquid chromatography (HPLC) and diode array detection (DAD), to evaluate the influence of mixed functionalization of the MOF on the analytical performance of the entire microextraction method. Eight organic pollutants of different natures were studied, using a concentration level of 5 µg· L⁻¹ to mimic contaminated waters. Target pollutants included carbamazepine, 4-cumylphenol, benzophenone-3, 4-tert-octylphenol, 4-octylphenol, chrysene, indeno(1,2,3-cd)pyrene, and triclosan, as representatives of drugs, phenols, polycyclic aromatic hydrocarbons, and disinfectants. Structurally, they differ in size and some of them present polar groups able to form H-bond interactions, either as donors (-NH₂) or acceptors (-NO₂), permitting us to evaluate possible interactions between MOF pore functionalities and analytes’ groups. As a result, extraction efficiencies can reach values of up to 60%, despite employing a microextraction approach, with four main trends of behavior being observed, depending on the analyte and the MOF. Full article

(This article belongs to the Special Issue Metal Organic Frameworks: Synthesis and Application)

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14 pages, 2995 KiB

Open AccessArticle

Facile Preparation of Metal-Organic Framework (MIL-125)/Chitosan Beads for Adsorption of Pb(II) from Aqueous Solutions

by Xue-Xue Liang, Nan Wang, You-Le Qu, Li-Ye Yang, Yang-Guang Wang and Xiao-Kun Ouyang

Molecules 2018, 23(7), 1524; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules23071524 - 25 Jun 2018

Cited by 48 | Viewed by 6205

Abstract

In this study, novel composite titanium-based metal-organic framework (MOF) beads were synthesized from titanium based metal organic framework MIL-125 and chitosan (CS) and used to remove Pb(II) from wastewater. The MIL-125-CS beads were prepared by combining the titanium-based MIL-125 MOF and chitosan using a template-free solvothermal approach under ambient conditions. The surface and elemental properties of these beads were analyzed using scanning electron microscopy, Fourier transform infrared and X-ray photoelectron spectroscopies, as well as thermal gravimetric analysis. Moreover, a series of experiments designed to determine the influences of factors such as initial Pb(II) concentration, pH, reaction time and adsorption temperature was conducted. Notably, it was found that the adsorption of Pb(II) onto the MIL-125-CS beads reached equilibrium in 180 min to a level of 407.50 mg/g at ambient temperature. In addition, kinetic and equilibrium experiments provided data that were fit to the Langmuir isotherm model and pseudo-second-order kinetics. Furthermore, reusability tests showed that MIL-125-CS retained 85% of its Pb(II)-removal capacity after five reuse cycles. All in all, we believe that the developed MIL-125-CS beads are a promising adsorbent material for the remediation of environmental water polluted by heavy metal ions. Full article

(This article belongs to the Special Issue Metal Organic Frameworks: Synthesis and Application)

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Review

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27 pages, 4348 KiB

Open AccessReview

Novel Approaches Utilizing Metal-Organic Framework Composites for the Extraction of Organic Compounds and Metal Traces from Fish and Seafood

by Sofia C. Vardali, Natalia Manousi, Mariusz Barczak and Dimitrios A. Giannakoudakis

Molecules 2020, 25(3), 513; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25030513 - 24 Jan 2020

Cited by 32 | Viewed by 6098

Abstract

The determination of organic and inorganic pollutants in fish samples is a complex and demanding process, due to their high protein and fat content. Various novel sorbents including graphene, graphene oxide, molecular imprinted polymers, carbon nanotubes and metal-organic frameworks (MOFs) have been reported for the extraction and preconcentration of a wide range of contaminants from fish tissue. MOFs are crystalline porous materials that are composed of metal ions or clusters coordinated with organic linkers. Those materials exhibit extraordinary properties including high surface area, tunable pore size as well as good thermal and chemical stability. Therefore, metal-organic frameworks have been recently used in many fields of analytical chemistry including sample pretreatment, fabrication of stationary phases and chiral separations. Various MOFs, and especially their composites or hybrids, have been successfully utilized for the sample preparation of fish samples for the determination of organic (i.e., antibiotics, antimicrobial compounds, polycyclic aromatic hydrocarbons, etc.) and inorganic pollutants (i.e., mercury, palladium, cadmium, lead, etc.) as such or after functionalization with organic compounds. Full article

(This article belongs to the Special Issue Metal Organic Frameworks: Synthesis and Application)

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28 pages, 4061 KiB

Open AccessFeature PaperReview

Polymer/Metal Organic Framework (MOF) Nanocomposites for Biomedical Applications

by Dimitrios Giliopoulos, Alexandra Zamboulis, Dimitrios Giannakoudakis, Dimitrios Bikiaris and Konstantinos Triantafyllidis

Molecules 2020, 25(1), 185; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25010185 - 01 Jan 2020

Cited by 170 | Viewed by 19606

Abstract

The utilization of polymer/metal organic framework (MOF) nanocomposites in various biomedical applications has been widely studied due to their unique properties that arise from MOFs or hybrid composite systems. This review focuses on the types of polymer/MOF nanocomposites used in drug delivery and imaging applications. Initially, a comprehensive introduction to the synthesis and structure of MOFs and bio-MOFs is presented. Subsequently, the properties and the performance of polymer/MOF nanocomposites used in these applications are examined, in relation to the approach applied for their synthesis: (i) non-covalent attachment, (ii) covalent attachment, (iii) polymer coordination to metal ions, (iv) MOF encapsulation in polymers, and (v) other strategies. A critical comparison and discussion of the effectiveness of polymer/MOF nanocomposites regarding their synthesis methods and their structural characteristics is presented. Full article

(This article belongs to the Special Issue Metal Organic Frameworks: Synthesis and Application)

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21 pages, 1751 KiB

Open AccessFeature PaperReview

Extraction of Metal Ions with Metal–Organic Frameworks

by Natalia Manousi, Dimitrios A. Giannakoudakis, Erwin Rosenberg and George A. Zachariadis

Molecules 2019, 24(24), 4605; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules24244605 - 16 Dec 2019

Cited by 57 | Viewed by 8309

Abstract

Metal–organic frameworks (MOFs) are crystalline porous materials composed of metal ions or clusters coordinated with organic linkers. Due to their extraordinary properties such as high porosity with homogeneous and tunable in size pores/cages, as well as high thermal and chemical stability, MOFs have gained attention in diverse analytical applications. MOFs have been coupled with a wide variety of extraction techniques including solid-phase extraction (SPE), dispersive solid-phase extraction (d-SPE), and magnetic solid-phase extraction (MSPE) for the extraction and preconcentration of metal ions from complex matrices. The low concentration levels of metal ions in real samples including food samples, environmental samples, and biological samples, as well as the increased number of potentially interfering ions, make the determination of trace levels of metal ions still challenging. A wide variety of MOF materials have been employed for the extraction of metals from sample matrices prior to their determination with spectrometric techniques. Full article

(This article belongs to the Special Issue Metal Organic Frameworks: Synthesis and Application)

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23 pages, 2629 KiB

Open AccessReview

Metal Organic Frameworks as Desulfurization Adsorbents of DBT and 4,6-DMDBT from Fuels

by Zoi-Christina Kampouraki, Dimitrios A. Giannakoudakis, Vaishakh Nair, Ahmad Hosseini-Bandegharaei, Juan Carlos Colmenares and Eleni A. Deliyanni

Molecules 2019, 24(24), 4525; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules24244525 - 10 Dec 2019

Cited by 59 | Viewed by 7835

Abstract

Ultradeep desulfurization of fuels is a method of enormous demand due to the generation of harmful compounds during the burning of sulfur-containing fuels, which are a major source of environmental pollution. Among the various desulfurization methods in application, adsorptive desulfurization (ADS) has low energy demand and is feasible to be employed at ambient conditions without the addition of chemicals. The most crucial factor for ADS application is the selection of the adsorbent, and, currently, a new family of porous materials, metal organic frameworks (MOFs), has proved to be very effective towards this direction. In the current review, applications of MOFs and their functionalized composites for ADS are presented and discussed, as well as the main desulfurization mechanisms reported for the removal of thiophenic compounds by various frameworks. Prospective methods regarding the further improvement of MOF’s desulfurization capability are also suggested. Full article

(This article belongs to the Special Issue Metal Organic Frameworks: Synthesis and Application)

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21 pages, 909 KiB

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Applications of Metal-Organic Frameworks in Food Sample Preparation

by Natalia Manousi, George A. Zachariadis, Eleni A. Deliyanni and Victoria F. Samanidou

Molecules 2018, 23(11), 2896; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules23112896 - 06 Nov 2018

Cited by 60 | Viewed by 6292

Abstract

Food samples such as milk, beverages, meat and chicken products, fish, etc. are complex and demanding matrices. Various novel materials such as molecular imprinted polymers (MIPs), carbon-based nanomaterials carbon nanotubes, graphene oxide and metal-organic frameworks (MOFs) have been recently introduced in sample preparation to improve clean up as well as to achieve better recoveries, all complying with green analytical chemistry demands. Metal-organic frameworks are hybrid organic inorganic materials, which have been used for gas storage, separation, catalysis and drug delivery. The last few years MOFs have been used for sample preparation of pharmaceutical, environmental samples and food matrices. Due to their high surface area MOFs can be used as adsorbents for the development of sample preparation techniques of food matrices prior to their analysis with chromatographic and spectrometric techniques with great performance characteristics. Full article

(This article belongs to the Special Issue Metal Organic Frameworks: Synthesis and Application)

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