molecules-logo

Journal Browser

Journal Browser

Special Issue "Metal Organic Frameworks: Synthesis and Application"

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

Deadline for manuscript submissions: closed (15 September 2019).

Printed Edition Available!
A printed edition of this Special Issue is available here.

Special Issue Editors

Prof. Dr. Victoria Samanidou
Website
Guest Editor
Laboratory of Analytical Chemistry, School of Chemistry, Aristotle University of Thessaloniki, Greece
Interests: analytical chemistry; sample preparation; separation techniques; HPLC; extraction techniques; microextraction; green analytical methodologies; method validation; method development; sorptive extraction
Special Issues and Collections in MDPI journals
Prof. Dr. Eleni Deliyanni
Website
Guest Editor
Department: Department of Chemistry, Aristotle University of Thessaloniki, Thessaloniki, Greece
Interests: adsorption/advanced oxidation processes in environmental applications; synthesis, surface modification, and surface characterization of materials; carbon/graphite oxide materials; desulfurization of fuels
Special Issues and Collections in MDPI journals

Special Issue Information

Dear Colleagues,

Metalorganic 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

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 papers will be 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. Molecules 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 2000 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 framework
  • catalysis
  • sample preparation
  • sensors
  • gas extraction
  • sorptive extraction

Related Special Issue

Published Papers (11 papers)

Order results
Result details
Select all
Export citation of selected articles as:

Editorial

Jump to: Research, Review

Open AccessEditorial
Metal Organic Frameworks: Synthesis and Application
Molecules 2020, 25(4), 960; https://doi.org/10.3390/molecules25040960 - 20 Feb 2020
Abstract
The concept of metal–organic frameworks (MOFs) was first introduced in 1990; nowadays they are among the most promising novel materials [...] Full article

Research

Jump to: Editorial, Review

Open AccessFeature PaperCommunication
Hydrogen-Bonding Linkers Yield a Large-Pore, Non-Catenated, Metal-Organic Framework with pcu Topology
Molecules 2020, 25(3), 697; https://doi.org/10.3390/molecules25030697 - 06 Feb 2020
Cited by 1
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 [...] Read more.
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
Show Figures

Graphical abstract

Open AccessArticle
Dual Emission in a Ligand and Metal Co-Doped Lanthanide-Organic Framework: Color Tuning and Temperature Dependent Luminescence
Molecules 2020, 25(3), 523; https://doi.org/10.3390/molecules25030523 - 25 Jan 2020
Cited by 1
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 [...] Read more.
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
Show Figures

Graphical abstract

Open AccessFeature PaperArticle
Building MOF Nanocomposites with Oxidized Graphitic Carbon Nitride Nanospheres: The Effect of Framework Geometry on the Structural Heterogeneity
Molecules 2019, 24(24), 4529; https://doi.org/10.3390/molecules24244529 - 11 Dec 2019
Cited by 5
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 [...] Read more.
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
Show Figures

Graphical abstract

Open AccessFeature PaperArticle
Mixed Functionalization of Organic Ligands in UiO-66: A Tool to Design Metal–Organic Frameworks for Tailored Microextraction
Molecules 2019, 24(20), 3656; https://doi.org/10.3390/molecules24203656 - 10 Oct 2019
Cited by 4
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 [...] Read more.
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
Show Figures

Graphical abstract

Open AccessArticle
Facile Preparation of Metal-Organic Framework (MIL-125)/Chitosan Beads for Adsorption of Pb(II) from Aqueous Solutions
Molecules 2018, 23(7), 1524; https://doi.org/10.3390/molecules23071524 - 25 Jun 2018
Cited by 13
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 [...] Read more.
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
Show Figures

Figure 1

Review

Jump to: Editorial, Research

Open AccessReview
Novel Approaches Utilizing Metal-Organic Framework Composites for the Extraction of Organic Compounds and Metal Traces from Fish and Seafood
Molecules 2020, 25(3), 513; https://doi.org/10.3390/molecules25030513 - 24 Jan 2020
Cited by 3
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 [...] Read more.
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
Show Figures

Graphical abstract

Open AccessFeature PaperReview
Polymer/Metal Organic Framework (MOF) Nanocomposites for Biomedical Applications
Molecules 2020, 25(1), 185; https://doi.org/10.3390/molecules25010185 - 01 Jan 2020
Cited by 5
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 [...] Read more.
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
Show Figures

Figure 1

Open AccessFeature PaperReview
Extraction of Metal Ions with Metal–Organic Frameworks
Molecules 2019, 24(24), 4605; https://doi.org/10.3390/molecules24244605 - 16 Dec 2019
Cited by 6
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 [...] Read more.
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
Show Figures

Graphical abstract

Open AccessReview
Metal Organic Frameworks as Desulfurization Adsorbents of DBT and 4,6-DMDBT from Fuels
Molecules 2019, 24(24), 4525; https://doi.org/10.3390/molecules24244525 - 10 Dec 2019
Cited by 2
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 [...] Read more.
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
Show Figures

Graphical abstract

Open AccessReview
Applications of Metal-Organic Frameworks in Food Sample Preparation
Molecules 2018, 23(11), 2896; https://doi.org/10.3390/molecules23112896 - 06 Nov 2018
Cited by 12
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 [...] Read more.
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
Show Figures

Figure 1

Back to TopTop