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Special Issue "Functional Metal-Organic Framework Based Materials"

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

Deadline for manuscript submissions: closed (15 August 2020).

Special Issue Editors

Dr. Luis Cunha-Silva
E-Mail Website1 Website2
Guest Editor
LAQV-REQUIMTE Associate Laboratory, University of Porto, 4169-007 Porto, Portugal
Interests: materials science and catalysis; coordination and inorganic chemistry; multifunctional metal-organic frameworks; high nuclearity coordination complexes; sustainable crystalline coordination polymers; structural chemistry; X-ray diffraction analysis
Special Issues, Collections and Topics in MDPI journals
Dr. Filipe Alexandre Almeida Paz
E-Mail Website
Guest Editor
Department of Chemistry, CICECO−Aveiro Institute of Materials, University of Aveiro, 3810-193 Aveiro, Portugal
Interests: design of functional metal-organic frameworks; catalysis; photoluminescence; proton conductivity; new synthetic methods of MOFs; sensing; interconvertible MOFs; sustainable synthesis methods
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

In the last two decades, research in metal-organic frameworks (MOFs) and porous coordination polymers (PCPs) changed the way chemists looked into traditional coordination chemistry. The rapid and widespread interest in these compounds, drastically motivated by the symbiotic combination of organic and inorganic components, rapidly evolved into their possible technological application in gas sorption/separation, catalysis, chemical sensing, energy storage, and conversion among many others.

The enormous potential in distinct scientific areas arises from mostly from their unique structural features, particularly well-defined crystalline structures, adjustable pore topology, ultra-high surface areas, and excellent tailorability. Thus, the initial scientific drive for unique and exotic crystal structures remains intrinsically connected to this research field. More recently, the functionality and potential applicability of MOFs and PCPs have been directed towards the preparation of MOF-based compounds and materials: post-synthetic modified MOFs, [email protected], MOFs/substrates, and pyrolytic MOFs.

The present Special Issue aims to assemble the recent relevant scientific achievements in the field of functional pristine MOFs and MOF-derived materials. The Special Issue will significantly benefit from the simultaneous contribution of original research articles as well of pertinent and critical review articles in this scientific field.

Dr. Luís Cunha Silva
Dr. Filipe Alexandre Almeida Paz
Guest Editors

Manuscript Submission Information

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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

  • Exotic MOF architectures
  • Modular assembly of MOFs
  • Photoluminescence
  • Gas separation and storage
  • MOFs for sensing applications
  • MOFs for energy conversion
  • Defects and MOFs and their properties
  • Ferroelectrics in MOFs
  • New methods of synthesis of MOFs
  • MOFs as efficient catalysts
  • Post-synthetic modification of MOFs

Published Papers (9 papers)

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Research

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Article
Sustainable Route for Synthesizing Aluminosilicate EU-1 Zeolite
Molecules 2021, 26(5), 1462; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26051462 - 08 Mar 2021
Viewed by 547
Abstract
Developing sustainable routes for the synthesis of zeolites is still a vital and challenging task in zeolite scientific community. One of the typical examples is sustainable synthesis of aluminosilicate EU-1 zeolite, which is not very efficient and environmental-unfriendly under hydrothermal condition due to [...] Read more.
Developing sustainable routes for the synthesis of zeolites is still a vital and challenging task in zeolite scientific community. One of the typical examples is sustainable synthesis of aluminosilicate EU-1 zeolite, which is not very efficient and environmental-unfriendly under hydrothermal condition due to the use of a large amount of water as solvent. Herein, we report a sustainable synthesis route for aluminosilicate EU-1 zeolite without the use of solvent for the first time. The physicochemical properties of the obtained EU-1 zeolite are characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetry-differential thermal analysis (TG-DTA), N2 sorption, inductively coupled plasma (ICP) analysis, and solid nuclear magnetic resonance (NMR), which show the product has high crystallinity, uniform morphology, large BET surface area, and four-coordinated aluminum species. Moreover, the impact of synthesis conditions is investigated in detail. The sustainable synthesis of aluminosilicate EU-1 zeolite under solvent-free Full article
(This article belongs to the Special Issue Functional Metal-Organic Framework Based Materials)
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Article
A Stable Coordination Polymer Based on Rod-Like Silver(I) Nodes with Contiguous Ag-S Bonding
Molecules 2020, 25(19), 4548; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25194548 - 04 Oct 2020
Viewed by 682
Abstract
Silver(I)-based coordination polymers or metal-organic frameworks (MOFs) display useful antibacterial properties, whereby distinct materials with different bonding can afford control over the release of silver(I) ions. Such silver(I) materials are comprised of discrete secondary building units (SBUs), and typically formed with ligands possessing [...] Read more.
Silver(I)-based coordination polymers or metal-organic frameworks (MOFs) display useful antibacterial properties, whereby distinct materials with different bonding can afford control over the release of silver(I) ions. Such silver(I) materials are comprised of discrete secondary building units (SBUs), and typically formed with ligands possessing only soft or borderline donors. We postulated that a linker with four potential donor groups, comprising carboxylate and soft thioether donors, 2,5-bis (allylsulfanyl) benzene dicarboxylic acid (ASBDC), could be used to form stable, highly connected coordination polymers with silver(I). Here, we describe the synthesis of a new material, (Ag2(ASBDC)), which possesses a rod-like metal node-based 3D honeycomb structure, strongly π-stacked linkers, and steric bulk to protect the node. Due to the rod-like metal node and the blocking afforded by the ordered allyl groups, the material displays notable thermal and moisture stability. An interesting structural feature of (Ag2(ASBDC)) is contiguous Ag–S bonding, essentially a helical silver chalcogenide wire, which extends through the structure. These interesting structural features, coupled with the relative ease by which MOFs made with linear dicarboxylate linkers can be reticulated, suggests this may be a structure type worthy of further investigation. Full article
(This article belongs to the Special Issue Functional Metal-Organic Framework Based Materials)
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Article
Proton Conductive Zr-Phosphonate UPG-1—Aminoacid Insertion as Proton Carrier Stabilizer
Molecules 2020, 25(15), 3519; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25153519 - 31 Jul 2020
Cited by 1 | Viewed by 1446
Abstract
Proton exchange membrane fuel cells (PEMFCs) are an attractive green technology for energy generation. The poor stability and performances under working conditions of the current electrolytes are their major drawbacks. Metal-Organic Frameworks (MOFs) have recently emerged as an alternative to overcome these issues. [...] Read more.
Proton exchange membrane fuel cells (PEMFCs) are an attractive green technology for energy generation. The poor stability and performances under working conditions of the current electrolytes are their major drawbacks. Metal-Organic Frameworks (MOFs) have recently emerged as an alternative to overcome these issues. Here, we propose a robust Zr-phosphonate MOF (UPG-1) bearing labile protons able to act a priori as an efficient electrolyte in PEMFCs. Further, in an attempt to further enhance the stability and conductivity of UPG-1, a proton carrier (the amino acid Lysine, Lys) was successfully encapsulated within its porosity. The behaviors of both solids as an electrolyte were investigated by a complete experimental (impedance spectroscopy, water sorption) and computational approach (MonteCarlo, water sorption). Compared with the pristine UPG-1, the newly prepared [email protected] composite showed similar proton conductivity but a higher stability, which allows a better cyclability. This improved cyclability is mainly related to the different hydrophobic-hydrophilic balance of the [email protected] and UPG-1 and the steric protection of the reactive sites of the MOF by the Lys. Full article
(This article belongs to the Special Issue Functional Metal-Organic Framework Based Materials)
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Article
Coordination Polymers Based on a Biphenyl Tetraphosphonate Linker: Synthesis Control and Photoluminescence
Molecules 2020, 25(8), 1835; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25081835 - 16 Apr 2020
Viewed by 930
Abstract
In this work, we used the rigid tetrapodal organic linker, [1,1′-biphenyl]-3,3′,5,5′-tetrayltetrakis(phosphonic acid) (H8btp), for the preparation of two lanthanide–organic framework families of compounds: layered [Ln7(H5btp)4(H5.5btp)2(H6btp)2(H2O) [...] Read more.
In this work, we used the rigid tetrapodal organic linker, [1,1′-biphenyl]-3,3′,5,5′-tetrayltetrakis(phosphonic acid) (H8btp), for the preparation of two lanthanide–organic framework families of compounds: layered [Ln7(H5btp)4(H5.5btp)2(H6btp)2(H2O)12]∙23.5H2O∙MeOH [where Ln3+ = Eu3+ (1Eu) and Gd3+ (1Gd)], prepared using microwave-irradiation followed by slow evaporation; 3D [Ln4(H3btp)(H4btp)(H5btp)(H2O)8]∙3H2O [where Ln3+ = Ce3+ (2Ce), Pr3+ (2Pr), and Nd3+ (2Nd)], obtained from conventional hydro(solvo)thermal synthesis. It is shown that in this system, by carefully selecting the synthetic method and the metal centers, one can increase the dimensionality of the materials, also increasing structural robustness (particularly to the release of the various solvent molecules). Compound 1 is composed of 2D layers stacked on top of each other and maintained by weak π–π interactions, with each layer formed by discrete 1D organic cylinders stacked in a typical brick-wall-like fashion, with water molecules occupying the free space in-between cylinders. Compound 2, on the other hand, is a 3D structure with small channels filled with crystallization water molecules. A full solid-state characterization of 1 and 2 is presented (FT-IR spectroscopy, SEM microscopy, thermogravimetric studies, powder X-ray diffraction and thermodiffractometry). The photoluminescence of 1Eu was investigated. Full article
(This article belongs to the Special Issue Functional Metal-Organic Framework Based Materials)
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Article
From Discrete Complexes to Metal–Organic Layered Materials: Remarkable Hydrogen Bonding Frameworks
Molecules 2020, 25(6), 1353; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25061353 - 16 Mar 2020
Cited by 2 | Viewed by 767
Abstract
A series of metal–organic coordination complexes based on alkaline-earth metal centers [Mg(II), Ca(II), and Ba(II)] and the ligand 5-aminoisophthalate (aip2−) revealed notable structural diversity, both in the materials’ dimensionality and in their hydrogen bonding networks: [Mg(H2O)6]∙[Mg2 [...] Read more.
A series of metal–organic coordination complexes based on alkaline-earth metal centers [Mg(II), Ca(II), and Ba(II)] and the ligand 5-aminoisophthalate (aip2−) revealed notable structural diversity, both in the materials’ dimensionality and in their hydrogen bonding networks: [Mg(H2O)6]∙[Mg2(Haip)(H2O)10]∙(Haip)∙3(aip)∙10(H2O) (1) and [Mg(aip)(phen)(H2O)2]∙(H2O) (2) were isolated as discrete complexes (0D); [Ca(aip)(H2O)2]∙(H2O) (3), [Ca(aip)(phen)(H2O)2]∙(phen)∙(H2O) (4), and [Ba2(aip)2(phen)2(H2O)7]∙2(phen)∙2(H2O) (5) revealed metal–organic chain (1D) structures, while the [Ba(aip)(H2O)] (6) showed a metal–organic layered (2D) arrangement. Furthermore, most of these metal–organic coordination materials revealed interesting thermal stability properties, being stable at temperatures up to 450 °C. Full article
(This article belongs to the Special Issue Functional Metal-Organic Framework Based Materials)
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Article
Metal-Organic Frameworks of MIL-100(Fe, Cr) and MIL-101(Cr) for Aromatic Amines Adsorption from Aqueous Solutions
Molecules 2019, 24(20), 3718; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules24203718 - 16 Oct 2019
Cited by 10 | Viewed by 2005
Abstract
MIL-100(Fe, Cr) and MIL-101(Cr) were synthesized by the hydrothermal method and applied to the adsorptions of five aromatic amines from aqueous solutions. These three metal-organic frameworks (MOFs) were well characterized by powder X-ray diffraction (PXRD), scanning electron microscope (SEM), transmission electron microscope (TEM), [...] Read more.
MIL-100(Fe, Cr) and MIL-101(Cr) were synthesized by the hydrothermal method and applied to the adsorptions of five aromatic amines from aqueous solutions. These three metal-organic frameworks (MOFs) were well characterized by powder X-ray diffraction (PXRD), scanning electron microscope (SEM), transmission electron microscope (TEM), thermogravimetric analysis (TGA) and surface area analysis. The adsorption mechanism of three MOFs and the effects of the structures of MOFs on the adsorption of aromatic amines were discussed. The results show that the cavity system and suitable hydrogen bond acceptor were important factors for the adsorption for five aromatic amines of aniline, 1-naphthalamine, o-toluidine, 2-amino-4-nitrotoluene and 2-nitroaniline: (a) the saturated adsorption capacity of aniline, 1-naphthylamine and o-toluidine on MIL-100(Fe) were 52.0, 53.4 and 49.6 mg/g, respectively, which can be attributed to the intermolecular hydrogen bond interaction and cavity system diffusion. (b) The adsorption capacity of 2-nitroaniline and 2-amino-4-nitrotoluene on MIL-101(Cr) were 54.3 and 25.0 mg/g, respectively, which can be attributed to the more suitable pore size of MIL-101(Cr) than that of MIL-100(Fe, Cr). The MOFs of MIL-100(Fe) and MIL-101(Cr) can be potential materials for removing aromatic amines from aqueous solutions. Full article
(This article belongs to the Special Issue Functional Metal-Organic Framework Based Materials)
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Article
Structural Transformations in the Thermal Dehydration of [Cu2(bpa)(btec)(H2O)4]n Coordination Polymer
Molecules 2019, 24(9), 1840; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules24091840 - 13 May 2019
Cited by 1 | Viewed by 1507
Abstract
Reactions between pyridinic ligands such as 1,2-bis(4-pyridyl)ethane (bpa) and transition metal cations are a very widespread technique to produce extended coordination polymers such as Metal-Organic Frameworks. In combination with a second ligand these systems could present different topologies and behaviors. In [...] Read more.
Reactions between pyridinic ligands such as 1,2-bis(4-pyridyl)ethane (bpa) and transition metal cations are a very widespread technique to produce extended coordination polymers such as Metal-Organic Frameworks. In combination with a second ligand these systems could present different topologies and behaviors. In this context, the use of 1,2,4,5-benzenetetracarboxylic acid (H4btec) gave us a novel 2D compound, [Cu2(bpa)(btec)(H2O)4]n (1), which was prepared by microwave-assisted synthesis and structurally characterized by means of single crystal X-ray diffraction. Its thermal behavior was analyzed through thermogravimetric analysis and variable temperature powder X-ray diffraction, concluding that thermal stability is influenced by the coordination water molecules, allowing two sequential thermochromic phase transformations to take place. These transformations were monitored by electronic paramagnetic resonance spectroscopy and magnetic susceptibility measurements. In addition, the crystal structure of the anhydrous compound [Cu2(bpa)(btec)]n (1.ah) was determined. Finally, a topological study was carried out for the bpa ligand considering all the structures deposited in the Cambridge Structural Databased. More than 1000 structures were analyzed and classified into 17 different topologies, according to the role of the ligand. Full article
(This article belongs to the Special Issue Functional Metal-Organic Framework Based Materials)
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Article
New Copper(II) Coordination Compounds Assembled from Multifunctional Pyridine-Carboxylate Blocks: Synthesis, Structures, and Catalytic Activity in Cycloalkane Oxidation
Molecules 2019, 24(1), 6; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules24010006 - 20 Dec 2018
Cited by 16 | Viewed by 2148
Abstract
Two new copper(II) coordination compounds, namely a 1D coordination polymer [Cu(µ-cpna)(phen)(H2O)]n (1) and a discrete tetracopper(II) derivative [Cu(phen)2(H2O)]2[Cu2(µ-Hdppa)2(Hdppa)2] (2), were hydrothermally synthesized from copper(II) [...] Read more.
Two new copper(II) coordination compounds, namely a 1D coordination polymer [Cu(µ-cpna)(phen)(H2O)]n (1) and a discrete tetracopper(II) derivative [Cu(phen)2(H2O)]2[Cu2(µ-Hdppa)2(Hdppa)2] (2), were hydrothermally synthesized from copper(II) chloride as a metal source, 5-(4-carboxyphenoxy)nicotinic acid (H2cpna) or 5-(3,4-dicarboxylphenyl)picolinic acid (H3dppa) as a principal building block, and 1,10-phenanthroline (phen) as a crystallization mediator. Compounds 1 and 2 were isolated as air-stable microcrystalline solids and fully characterized by elemental and thermogravimetric analyses, IR spectroscopy, powder and single-crystal X-ray diffraction. In the solid state, the structure of 1 discloses the linear interdigitated 1D coordination polymer chains with the 2C1 topology. The crystal structure of an ionic derivative 2 shows that the mono- and dicopper(II) units are extended into the intricate 1D hydrogen-bonded chains with the SP 1-periodic net (4,4)(0,2) topology. Thermal stability and catalytic properties of 1 and 2 were also investigated. In fact, both Cu derivatives act as efficient homogeneous catalysts (catalyst precursors) for the mild oxidation of cycloalkanes by hydrogen peroxide to give the corresponding alcohols and ketones; the substrate scope and the effects of type and amount of acid promoter as well as bond-, regio-, and stereo-selectivity features were investigated. Full article
(This article belongs to the Special Issue Functional Metal-Organic Framework Based Materials)
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Review

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Review
Metal-Organic Framework-Based Engineered Materials—Fundamentals and Applications
Molecules 2020, 25(7), 1598; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25071598 - 31 Mar 2020
Cited by 22 | Viewed by 2682
Abstract
Metal-organic frameworks (MOFs) are a fascinating class of porous crystalline materials constructed by organic ligands and inorganic connectors. Owing to their noteworthy catalytic chemistry, and matching or compatible coordination with numerous materials, MOFs offer potential applications in diverse fields such as catalysis, proton [...] Read more.
Metal-organic frameworks (MOFs) are a fascinating class of porous crystalline materials constructed by organic ligands and inorganic connectors. Owing to their noteworthy catalytic chemistry, and matching or compatible coordination with numerous materials, MOFs offer potential applications in diverse fields such as catalysis, proton conduction, gas storage, drug delivery, sensing, separation and other related biotechnological and biomedical applications. Moreover, their designable structural topologies, high surface area, ultrahigh porosity, and tunable functionalities all make them excellent materials of interests for nanoscale applications. Herein, an effort has been to summarize the current advancement of MOF-based materials (i.e., pristine MOFs, MOF derivatives, or MOF composites) for electrocatalysis, photocatalysis, and biocatalysis. In the first part, we discussed the electrocatalytic behavior of various MOFs, such as oxidation and reduction candidates for different types of chemical reactions. The second section emphasizes on the photocatalytic performance of various MOFs as potential candidates for light-driven reactions, including photocatalytic degradation of various contaminants, CO2 reduction, and water splitting. Applications of MOFs-based porous materials in the biomedical sector, such as drug delivery, sensing and biosensing, antibacterial agents, and biomimetic systems for various biological species is discussed in the third part. Finally, the concluding points, challenges, and future prospects regarding MOFs or MOF-based materials for catalytic applications are also highlighted. Full article
(This article belongs to the Special Issue Functional Metal-Organic Framework Based Materials)
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