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Special Issue "Metal Organic Framework Materials"

A special issue of Materials (ISSN 1996-1944).

Deadline for manuscript submissions: closed (31 May 2017)

Special Issue Editor

Guest Editor
Prof. Dr. Claudio Pettinari

Inorganic Chemistry Unit, School of Pharmacy-ICCOM-CNR Camerino, University of Camerino, via S. Agostino 1, 62032 Camerino, Italy
Website | E-Mail
Interests: homogeneous catalysis; metal-organic frameworks, small molecules activation, antitumor compounds, bioinorganic Models; chemistry of materials; organotin compounds, luminescent compounds

Special Issue Information

Dear Colleagues,

MOFs (Metal-Organic Frameworks) and PCPs (porous coordination polymers) are a class of crystalline microporous hybrid solids built of inorganic units (isolated cations, clusters, chains, or layers) connected through polytopic linkers (e.g. polycarboxylate), defining pores of various shapes and sizes. The potential applications of these hybrid solids lie in the area of gas storage and separation, water, air and fuel purification, catalysis, drug release, supercapacitors, and electrochemistry. Compared to their purely inorganic counterparts (zeolites), the great variety offered by the organic chemistry allows the systematic modification of their chemical composition, of their pores surface and, thus, finally, of their properties (very large surface area, sorption selectivity).

The focus of this Special Issue is on a description of recent potential and emerging applications of MOFs and PCPs, and also on recent advances of their uses as catalysts, biorelevant and sensing species, and in toxic gas removal. Articles describing relationships between molecular parameters and structures, preferred adsorption sites, and properties elucidated by using modern theoretical methods are welcome.

Prof. Dr. Claudio Pettinari
Guest Editor

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. Materials is an international peer-reviewed open access monthly 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 1500 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

  • MOFs
  • PCPs
  • gas-storage
  • catalysis
  • luminescent materials
  • sensors
  • biological applications

Published Papers (6 papers)

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Research

Open AccessArticle Preparation of Cationic MOFs with Mobile Anions by Anion Stripping to Remove 2,4-D from Water
Materials 2017, 10(8), 879; doi:10.3390/ma10080879
Received: 3 July 2017 / Revised: 18 July 2017 / Accepted: 24 July 2017 / Published: 30 July 2017
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Abstract
A cationic porous framework with mobile anions (MIL-101(Cr)-Cl) was easily and successfully synthesized by utilizing the stronger affinity of F to Al3+ than Cr3+ in the charge-balanced framework of MIL-101(Cr). The structure, morphology and porosity of MIL-101(Cr)-Cl were characterized. The
[...] Read more.
A cationic porous framework with mobile anions (MIL-101(Cr)-Cl) was easily and successfully synthesized by utilizing the stronger affinity of F to Al3+ than Cr3+ in the charge-balanced framework of MIL-101(Cr). The structure, morphology and porosity of MIL-101(Cr)-Cl were characterized. The obtained new materials retain the high surface area, good thermostability, and structure topology of MIL-101(Cr). With the mobile Cl anion, MIL-101(Cr)-Cl can be used as an ion-exchange material for anionic organic pollutions. In this work, 2,4-dichlorophenoxyacetic acid (2,4-D) was used as a model to test the absorption performance of this new material. This new material exhibited improved adsorbability compared to that of the original metal-organic frameworks (MOFs). At the same time, this material also shows high anti-interference performance with changing solution pH. Full article
(This article belongs to the Special Issue Metal Organic Framework Materials)
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Open AccessArticle Study of Adsorption and Desorption Performances of Zr-Based Metal–Organic Frameworks Using Paper Spray Mass Spectrometry
Materials 2017, 10(7), 769; doi:10.3390/ma10070769
Received: 11 June 2017 / Revised: 3 July 2017 / Accepted: 4 July 2017 / Published: 8 July 2017
Cited by 1 | PDF Full-text (3650 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
The dynamic pore systems and high surface areas of flexible metal–organic framework materials make them excellent candidates to be used in different kinds of adsorption processes. However, the adsorption and desorption behaviors of therapeutic drugs on metal–organic frameworks in solution are not fully
[...] Read more.
The dynamic pore systems and high surface areas of flexible metal–organic framework materials make them excellent candidates to be used in different kinds of adsorption processes. However, the adsorption and desorption behaviors of therapeutic drugs on metal–organic frameworks in solution are not fully developed. Here, we systematically investigated the adsorption and desorption behaviors of a typical therapeutic drug, verapamil, over several Zr-based metal–organic frameworks [e.g., Zr-FUM, UiO-66(Zr), UiO-66(Zr)-NH2 and UiO-66(Zr)-2COOH] as well as ZrO2 in an acetonitrile solution by using paper spray mass spectrometry. In contrast to other materials, UiO-66(Zr)-2COOH demonstrated a superior adsorption performance to verapamil due to their strong acid-base and/or hydrogen-bond interactions, and the adsorption process fitted well with the pseudo-second-order kinetic model. As verapamil-adsorbed materials were used for desorption experiments, ZrO2 demonstrated the most favorable desorption performance, whereas UiO-66(Zr)-2COOH yielded the poorest desorption capability. These Zr-based materials had also been coated at the surface with filter papers for the analysis of various drugs and proteins in the process of paper spray mass spectrometry. The results demonstrated that among the studied materials, ZrO2-coated paper gave the most favorable desorption performance as a pure drug solution, whereas the paper from UiO-66(Zr) demonstrated the optimal capability in the analyses of therapeutic drugs in a complex matrix (e.g., blood) and a protein (e.g., myoglobin). Full article
(This article belongs to the Special Issue Metal Organic Framework Materials)
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Open AccessFeature PaperArticle 4,2’:6’,4”- and 3,2’:6’,3”-Terpyridines: The Conflict between Well-Defined Vectorial Properties and Serendipity in the Assembly of 1D-, 2D- and 3D-Architectures
Materials 2017, 10(7), 728; doi:10.3390/ma10070728
Received: 12 June 2017 / Revised: 27 June 2017 / Accepted: 28 June 2017 / Published: 30 June 2017
Cited by 2 | PDF Full-text (3428 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
A comparative investigation of the coordination assemblies formed between Co(NCS)2 and two monotopic 4,2’:6’,4’’-terpyridine (4,2’:6’,4”-tpy) ligands or two related ditopic ligands is reported. Crystals were grown by layering MeOH solutions of Co(NCS)2 over a CHCl3 or 1,2-C6H4
[...] Read more.
A comparative investigation of the coordination assemblies formed between Co(NCS)2 and two monotopic 4,2’:6’,4’’-terpyridine (4,2’:6’,4”-tpy) ligands or two related ditopic ligands is reported. Crystals were grown by layering MeOH solutions of Co(NCS)2 over a CHCl3 or 1,2-C6H4Cl2 solution of the respective ligand at room temperature. With 4’-(2-methylpyrimidin-5-yl)-4,2’:6’,4”-terpyridine (6), the 1D-coordination polymer {[Co2(NCS)4(MeOH)4(6)2]∙2MeOH∙8H2O}n assembles with 6 coordinating only through the outer N-donors of the 4,2’:6’,4”-tpy unit; coordination by the MeOH solvent blocks two cobalt coordination sites preventing propagation in a higher-dimensional network. A combination of Co(NCS)2 and 1-(4,2‘:6’,4”-terpyridin-4’-yl)ferrocene (7) leads to {[Co(NCS)2(7)2]∙4CHCl3}n which contains a (4,4) net; the 2D-sheets associate through π-stacking interactions between ferrocenyl and pyridyl units. A 3D-framework is achieved through use of the ditopic ligand 1,4-bis(npropoxy)-2,5-bis(4,2’:6’,4”-terpyridin-4’-yl)benzene (8) which acts as a 4-connecting node in {[Co(NCS)2(8)2].2C6H4Cl2}n; the combination of metal and ligand planar 4-connecting nodes results in a {65.8} cds net. For a comparison with the coordinating abilities of the previously reported 1,4-bis(noctoxy)-2,5-bis(4,2’:6’,4”-terpyridin-4’-yl)benzene (3), a more flexible analogue 9 was prepared. {[Co(NCS)2(9)]∙2CHCl3}n contains a (4,4) net defined by both metal and ligand planar 4-connecting nodes. The noctoxy tails of 9 protrude from each side of the (4,4) net and thread through adjacent sheets; the arene-attached noctoxy chains associate through a combination of van der Waals and C–H...π interactions. Full article
(This article belongs to the Special Issue Metal Organic Framework Materials)
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Open AccessFeature PaperArticle Coordination Driven Capture of Nicotine Inside a Mesoporous MOF
Materials 2017, 10(7), 727; doi:10.3390/ma10070727
Received: 14 June 2017 / Revised: 23 June 2017 / Accepted: 27 June 2017 / Published: 30 June 2017
PDF Full-text (5246 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Metal organic frameworks (MOFs) are a wide class of crystalline porous polymers studied in many fields, ranging from catalysis to gas storage. In the past few years, MOFs have been studied for the encapsulation of organic or organometallic molecules and for the development
[...] Read more.
Metal organic frameworks (MOFs) are a wide class of crystalline porous polymers studied in many fields, ranging from catalysis to gas storage. In the past few years, MOFs have been studied for the encapsulation of organic or organometallic molecules and for the development of potential drug carriers. Here, we report on the study of two structurally-related mesoporous Cu-MOFs, namely PCN-6 and PCN-6′ (PCN stands for Porous Coordination Network), for nicotine trapping. Nicotine is a well-known alkaloid liquid molecule at room temperature, whose crystalline structure is still unknown. In this work, the loading process was monitored by electron ionization mass spectrometry by using a direct insertion probe (DIP-EI/MS), infrared (IR), and ultraviolet/visible (UV/VIS) analysis. Both nuclear magnetic resonance (NMR) spectroscopy and thermogravimetric (TGA) analysis showed evidence that nicotine trapping reaches remarkable uptakes up to 40 wt %. In the case of PCN-6@nicotine, X-ray structural resolution revealed that the guest uptake is triggered by coordination of the pyridine ring of nicotine to the copper nuclei of the paddle-wheel units composing the framework of PCN-6. Full article
(This article belongs to the Special Issue Metal Organic Framework Materials)
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Open AccessArticle Kinetic Analysis of the Uptake and Release of Fluorescein by Metal-Organic Framework Nanoparticles
Materials 2017, 10(2), 216; doi:10.3390/ma10020216
Received: 29 November 2016 / Revised: 3 February 2017 / Accepted: 9 February 2017 / Published: 22 February 2017
Cited by 1 | PDF Full-text (3377 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Metal-organic framework nanoparticles (MOF NPs) are promising guest-host materials with applications in separation, storage, catalysis, and drug delivery. However, on- and off-loading of guest molecules by porous MOF nanostructures are still poorly understood. Here we study uptake and release of fluorescein by two
[...] Read more.
Metal-organic framework nanoparticles (MOF NPs) are promising guest-host materials with applications in separation, storage, catalysis, and drug delivery. However, on- and off-loading of guest molecules by porous MOF nanostructures are still poorly understood. Here we study uptake and release of fluorescein by two representative MOF NPs, MIL-100(Fe) and MIL-101(Cr). Suspensions of these MOF NPs exhibit well-defined size distributions and crystallinity, as verified by electron microscopy, dynamic light scattering, and X-ray diffraction. Using absorbance spectroscopy the equilibrium dissociation constants and maximum numbers of adsorbed fluorescein molecules per NP were determined. Time-resolved fluorescence studies reveal that rates of release and loading are pH dependent. The kinetics observed are compared to theoretical estimates that account for bulk diffusion into NPs, and retarded internal diffusion and adsorption rates. Our study shows that, rather than being simple volumetric carriers, MOF-NPs are dominated by internal surface properties. The findings will help to optimize payload levels and develop release strategies that exploit varying pH for drug delivery. Full article
(This article belongs to the Special Issue Metal Organic Framework Materials)
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Open AccessArticle Adsorption Behavior of High Stable Zr-Based MOFs for the Removal of Acid Organic Dye from Water
Materials 2017, 10(2), 205; doi:10.3390/ma10020205
Received: 15 January 2017 / Revised: 9 February 2017 / Accepted: 15 February 2017 / Published: 20 February 2017
Cited by 2 | PDF Full-text (2591 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Zirconium based metal organic frameworks (Zr-MOFs) have become popular in engineering studies due to their high mechanical stability, thermostability and chemical stability. In our work, by using a theoretical kinetic adsorption isotherm, we can exert MOFs to an acid dye adsorption process, experimentally
[...] Read more.
Zirconium based metal organic frameworks (Zr-MOFs) have become popular in engineering studies due to their high mechanical stability, thermostability and chemical stability. In our work, by using a theoretical kinetic adsorption isotherm, we can exert MOFs to an acid dye adsorption process, experimentally exploring the adsorption of MOFs, their external behavior and internal mechanism. The results indicate their spontaneous and endothermic nature, and the maximum adsorption capacity of this material for acid orange 7 (AO7) could be up to 358 mg·g−1 at 318 K, estimated by the Langmuir isotherm model. This is ascribed to the presence of an open active metal site that significantly intensified the adsorption, by majorly increasing the interaction strength with the adsorbates. Additionally, the enhanced π delocalization and suitable pore size of UiO-66 gave rise to the highest host–guest interaction, which further improves both the adsorption capacity and separation selectivity at low concentrations. Furthermore, the stability of UiO-66 was actually verified for the first time, through comparing the structure of the samples before and after adsorption mainly by Powder X-ray diffraction and thermal gravimetric analysis. Full article
(This article belongs to the Special Issue Metal Organic Framework Materials)
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Planned Papers

The below list represents only planned manuscripts. Some of these manuscripts have not been received by the Editorial Office yet. Papers submitted to MDPI journals are subject to peer-review.

Title: Adsorption Behavior of High Stable Zr-based MOFs for Removal of Acid Organic Dye from Water
Author: Fang-Chang Tsai
Affiliation: Key Laboratory for the Green Preparation and Application of Functional Materials, Ministry of Education, Faculty of Materials Science & Engineering of Hubei University, Wuhan, China
Abstract: In our work, highly porous metal-organic framework (UiO-66) was successfully synthesized and applied to removal acid orange 7.  The adsorption behaviour and mechanism were discussed by the adsorption kinetics, adsorption isotherm as well as adsorption thermodynamics in detail. We can find that the adsorption is a spontaneous process on thermodynamics, and obey pseudo-second order kinetic model. The adsorption isotherm study reveals that the adsorption is well fitted by Langmuir isotherm model with monolayer adsorption, and the maximum adsorption capacity of this MOF material for AO7 is estimated up to be 358 mg g-1 at 318 K. Finally, the Lewis acid-base interaction between AO7 and UiO-66 is verified, in which the zirconium ions as open active site can coordinate with sulfosalt containing in AO7. The strength with the Lewis acid-base interaction of Zr-(-SO3-) is higher than Zr-(H2O) / Zr-(DMF) but less than Zr-(-CO2-). So, UiO-66 not only can effective remove AO7 from water and maintain the complete crystal structure. The zirconium ion with Lewis acid character in UiO-66 is encompassed with water molecule, because a lot of water molecule competes with AO7 molecule to impede the formation of complex between UiO-66 and AO7 during the initial period. Over time, the AO7 molecule spread to the surface of UiO-66, and replace the water molecule to form relatively stable complex compound.

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