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Applied Sciences
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Synthesis and Applications of Metal-Organic Frameworks (MOFs)
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Synthesis and Applications of Metal-Organic Frameworks (MOFs)

A special issue of Applied Sciences (ISSN 2076-3417). This special issue belongs to the section "Materials Science and Engineering".

Deadline for manuscript submissions: 20 July 2024 | Viewed by 15958

Special Issue Editors

Dr. Stephen David Worrall

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Guest Editor
Aston Institute of Materials Research, Aston University, Birmingham, UK
Interests: MOFs; electrochemistry; 2D materials; nanoporous materials; advanced materials; nanocomposites; thin film deposition; material characteristics; atmospheric chemistry
Dr. Julia Linnemann

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Guest Editor
Junior Research Group Shape-dependent electrochemistry, Chair of Analytical Chemistry II, Ruhr-University Bochum, Bochum, Germany
Interests: shape-dependent electrochemistry; energy storage and conversion; analytical electrochemical characterization; single-entity electrochemistry; electrochemical fabrication of 3-dimensional electrode architectures and coatings of functional materials such as metal-organic frameworks

Special Issue Information

Dear Colleagues,

Nanoporous metal–organic frameworks (MOFs) have generated huge research interest in a wide range of fields since their discovery at the turn of the millennium. Whilst this in part due to their record-breaking surface areas and porous volumes, their modular nature, providing almost limitless opportunities for chemical modification and functionalization, has widened their appeal to an even broader range of potential applications.

Many of these potential applications necessitate the MOF to be in the form of a thin film coating; as traditional solvothermal synthesis techniques are ill-equipped to meet this need, this has spurred research efforts in the development of alternative synthesis strategies. In particular, over the last decade, a variety of electrochemical methods for MOF synthesis have been developed, all with their own pros and cons. Work remains to be done in order to broaden the applicability of these methods to the synthesis of the huge family of MOF structures as well as to enable application-oriented designed film properties, e.g., by controlling crystal sizes, shape and intergrowth.

Electrochemical synthesis methods naturally yield MOFs as thin film coatings on conductive substrates, which is hugely advantageous for research into the potential electrochemical applications of MOFs. There is significant literature reporting the use of MOFs in a wide range of electrical applications, including supercapacitors, battery electrodes, electrochemical sensing and data storage, to name just a few, both in their “pure” MOF and also where they have been used as the precursor for the formation of porous carbons or porous metal oxides.

In this Special Issue, we seek to discuss the most recent advances both in the electrochemical synthesis of MOFs (including novel methods, adaptations of existing methods for specific MOFs and research into the understanding of the mechanisms behind the different methods) and in their use for any and all electrochemical and electrical applications (as pure MOF, in the form of composites or as a precursor for other porous materials). In this regard, studies addressing how structural and morphological properties of MOF crystals and the respective films they constitute relate to electrochemical performance are also highly appreciated.

Dr. Stephen David Worrall
Dr. Julia Linnemann
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 submissions that pass pre-check are 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. Applied Sciences 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 2400 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
  • MOF
  • electrochemical synthesis
  • anodic dissolution
  • cathodic deposition
  • electrophoretic deposition
  • supercapacitors
  • batteries
  • electrochemical sensing
  • data storage
  • electrochemical applications

Published Papers (7 papers)

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Research

13 pages, 2822 KiB  
Article
Structure Control Using Bioderived Solvents in Electrochemical Metal-Organic Framework Synthesis
by Meha Bhindi, Liam Massengo, James Hammerton, Matthew J. Derry and Stephen D. Worrall
Appl. Sci. 2023, 13(2), 720; https://doi.org/10.3390/app13020720 - 04 Jan 2023
Cited by 3 | Viewed by 1572
Abstract
Electrochemical synthesis of metal-organic frameworks (MOFs) has proven to possess many environmental advantages over traditional synthesis methods such as reduced energy use and shorter reaction times. However, the use of toxic, fossil fuel derived solvents such as N,N-dimethylformamide (DMF) presents [...] Read more.
Electrochemical synthesis of metal-organic frameworks (MOFs) has proven to possess many environmental advantages over traditional synthesis methods such as reduced energy use and shorter reaction times. However, the use of toxic, fossil fuel derived solvents such as N,N-dimethylformamide (DMF) presents a challenge to the environmental credentials of this method that has yet to be dealt with. Here, we investigate bioderived solvents, CyreneTM and γ-valerolactone (GVL), as an alternative for the synthesis of a range of MOFs via the anodic deposition method. The obtained MOF materials are characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM) to confirm their identities and morphologies and for comparison with MOFs synthesized using the traditional DMF-based solvent systems. When using CyreneTM and GVL solvents, crystalline MOF materials were obtained of comparable quality to those afforded using DMF. However, in several cases, using CyreneTM or GVL led to the formation of less stable, higher porosity MOF structures than those obtained using DMF, indicating that the larger bio solvent molecules may also play a templating role during the synthesis. This study successfully demonstrates the first-time electrochemical synthesis of MOFs has been performed using bio solvents and has highlighted that the use of bio solvents can provide a route to obtaining lower density, higher porosity MOF phases than those obtained using traditional solvents. Full article
(This article belongs to the Special Issue Synthesis and Applications of Metal-Organic Frameworks (MOFs))
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15 pages, 6255 KiB  
Article
Solid-Phase Extraction of Organic Dyes on Mixed-Ligand Zr(IV) Metal–Organic Framework
by Boris Kharisov, Oxana Kharissova, Vladimir Zhinzhilo, Julia Bryantseva and Igor Uflyand
Appl. Sci. 2022, 12(23), 12219; https://doi.org/10.3390/app122312219 - 29 Nov 2022
Cited by 2 | Viewed by 1235
Abstract
Currently, among the various areas of targeted wastewater treatment, great attention is being given by researchers to the solid-phase extraction of organic dyes using metal–organic frameworks (MOFs). In this work, a mixed-ligand Zr-MOF containing terephthalic acid and 1,10-phenanthroline as linkers was used for [...] Read more.
Currently, among the various areas of targeted wastewater treatment, great attention is being given by researchers to the solid-phase extraction of organic dyes using metal–organic frameworks (MOFs). In this work, a mixed-ligand Zr-MOF containing terephthalic acid and 1,10-phenanthroline as linkers was used for this purpose. The limiting adsorption of the dyes Congo red and methylene blue, according to experimental data, is 40 mg/g. The influence of various parameters (time, temperature, adsorbent dosage, pH, and coexisting ions) on adsorption characteristics was studied. The sorbent was tested for the removal of dyes from drinks in water and in artificial seawater. The possibility of the separation of dyes by column chromatography using a sorbent as a filler was studied. Full article
(This article belongs to the Special Issue Synthesis and Applications of Metal-Organic Frameworks (MOFs))
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14 pages, 2334 KiB  
Communication
ZIF-75 under Pressure: Negative Linear Compressibility and Pressure-Induced Instability
by Francisco Colmenero and Vicente Timón
Appl. Sci. 2022, 12(20), 10413; https://doi.org/10.3390/app122010413 - 15 Oct 2022
Cited by 6 | Viewed by 1518
Abstract
The behavior of the crystal structure of the zeolitic imidazolate framework ZIF-75 under pressure was studied by means of periodic density functional theory methods. Experimentally, it was shown that this material is tetragonal, space group I41/a at room temperature. However, [...] Read more.
The behavior of the crystal structure of the zeolitic imidazolate framework ZIF-75 under pressure was studied by means of periodic density functional theory methods. Experimentally, it was shown that this material is tetragonal, space group I41/a at room temperature. However, according to the calculations, at zero temperature this material is monoclinic, space group C2/c. Irrespective of the symmetry of the material, the results show that ZIF-75 exhibits a negative linear compressibility effect and is unstable under relatively small applied pressures of the order of 0.1 GPa. Full article
(This article belongs to the Special Issue Synthesis and Applications of Metal-Organic Frameworks (MOFs))
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11 pages, 1970 KiB  
Article
Adsorption of Methyl Orange on a Novel Palygorskite/UiO-66 Nanocomposite
by Ioanna A. Vasiliadou, Thaleia Ioannidou, Maria Anagnostopoulou, Antonios Polyzotou, Dimitrios Papoulis and Konstantinos C. Christoforidis
Appl. Sci. 2022, 12(15), 7468; https://doi.org/10.3390/app12157468 - 25 Jul 2022
Cited by 6 | Viewed by 1595
Abstract
Herein, a novel composite material containing UiO-66 and palygorskite (Pal) clay mineral was prepared using a facile one-pot synthesis process. The material was studied using a variety of techniques and applied as did not affect the structure of the metal-organic framework (MOF) part, [...] Read more.
Herein, a novel composite material containing UiO-66 and palygorskite (Pal) clay mineral was prepared using a facile one-pot synthesis process. The material was studied using a variety of techniques and applied as did not affect the structure of the metal-organic framework (MOF) part, but induced a small increase in specific surface area. The developed Pal/UiO-66 composite presented excellent adsorption efficiency against MO removal, as evidenced by detailed kinetic and isotherm experiments. An impressive maximum adsorption capacity at equilibrium was evidenced; 340 mg g−1 at pH = 5 and T = 25 °C. This corresponds to a 34.5 % increase compared with pure UiO-66, considering only the MOF content. Furthermore, the Pal/UiO-66 composite was proven stable and highly recyclable, losing less than 9% of the removal capacity after five consecutive cycles. The study highlights the synergistic effect of the coupling of MOF structures with low-cost and abundant clay minerals for the development of advanced absorbents. Full article
(This article belongs to the Special Issue Synthesis and Applications of Metal-Organic Frameworks (MOFs))
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17 pages, 4025 KiB  
Article
Controllable Synthesis of 1, 3, 5-tris (1H-benzo[d]imidazole-2-yl) Benzene-Based MOFs
by Sanjit Gaikwad, Ravi Kumar Cheedarala, Ranjit Gaikwad, Soonho Kim and Sangil Han
Appl. Sci. 2021, 11(21), 9856; https://doi.org/10.3390/app11219856 - 21 Oct 2021
Cited by 10 | Viewed by 2586
Abstract
The growing interest in metal–organic frameworks (MOFs) in both industrial and scientific circles has increased in the last twenty years, owing to their crystallinity, structural versatility, and controlled porosity. In this study, we present three novel MOFs obtained from the 1, 3, 5-tris [...] Read more.
The growing interest in metal–organic frameworks (MOFs) in both industrial and scientific circles has increased in the last twenty years, owing to their crystallinity, structural versatility, and controlled porosity. In this study, we present three novel MOFs obtained from the 1, 3, 5-tris (1H-benzo[d]imidazole-2-yl) benzene (TIBM) organic linker. The formed TIBM crystal powders were characterized by scanning electron microscopy (SEM) to estimate the morphology of the particles, powder X-ray diffraction (XRD) to confirm the crystal structure, Brunauer–Emmett–Teller (BET) method for structural analysis, and thermogravimetric measurements to examine the thermal stability. The TIBM-Cu MOF showed excellent CO2 (3.60 mmol/g) adsorption capacity at 1 bar and 298 K, because of the open Cu site, compared to TIBM-Cr (1.6 mmol/g) and TIBM-Al (2.1 mmol/g). Additionally, due to the high porosity (0.3–1.5 nm), TIBM-Cu MOF showed a considerable CO2/N2 selectivity (53) compared to TIBM-Al (35) and TIBM-Cr (10). Full article
(This article belongs to the Special Issue Synthesis and Applications of Metal-Organic Frameworks (MOFs))
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15 pages, 10014 KiB  
Article
Preparation and Application of ZIF-8 Thin Layers
by Martin Schernikau, Jakob Sablowski, Ignacio Guillermo Gonzalez Martinez, Simon Unz, Stefan Kaskel and Daria Mikhailova
Appl. Sci. 2021, 11(9), 4041; https://doi.org/10.3390/app11094041 - 29 Apr 2021
Cited by 7 | Viewed by 3504
Abstract
Herein we compare various preparation methods for thin ZIF-8 layers on a Cu substrate for application as a host material for omniphobic lubricant-infused surfaces. Such omniphobic surfaces can be used in thermal engineering applications, for example to achieve dropwise condensation or anti-fouling and [...] Read more.
Herein we compare various preparation methods for thin ZIF-8 layers on a Cu substrate for application as a host material for omniphobic lubricant-infused surfaces. Such omniphobic surfaces can be used in thermal engineering applications, for example to achieve dropwise condensation or anti-fouling and anti-icing surface properties. For these applications, a thin, conformal, homogeneous, mechanically and chemically stable coating is essential. In this study, thin ZIF-8 layers were deposited on a Cu substrate by different routes, such as (i) electrochemical anodic deposition on a Zn-covered Cu substrate, (ii) doctor blade technique for preparation of a composite layer containing PVDF binder and ZIF-8, as well as (iii) doctor blade technique for preparation of a two-layer composite on the Cu substrate containing a PVDF-film and a ZIF-8 layer. The morphology and topography of the coatings were compared by using profilometry, XRD, SEM and TEM techniques. After infusion with a perfluorinated oil, the wettability of the surfaces was assessed by contact angle measurements, and advantages of each preparation method were discussed. Full article
(This article belongs to the Special Issue Synthesis and Applications of Metal-Organic Frameworks (MOFs))
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12 pages, 3544 KiB  
Article
Electrosynthesis of HKUST-1 with Flow-Reactor Post-Processing
by Mikko Vepsäläinen, David S. Macedo, Huan Gong, Marta Rubio-Martinez, Bita Bayatsarmadi and Brandon He
Appl. Sci. 2021, 11(8), 3340; https://doi.org/10.3390/app11083340 - 08 Apr 2021
Cited by 9 | Viewed by 2391
Abstract
Electrochemical synthesis has been proposed as an efficient method for cost-effective and large-scale production of metal-organic frameworks (MOFs). This work investigates the combined electrochemical synthesis with flow synthesis post-treatment for the production of high surface area HKUST-1. The electrochemical synthesis process used in [...] Read more.
Electrochemical synthesis has been proposed as an efficient method for cost-effective and large-scale production of metal-organic frameworks (MOFs). This work investigates the combined electrochemical synthesis with flow synthesis post-treatment for the production of high surface area HKUST-1. The electrochemical synthesis process used in the experimental work did not require additional electrolytes or washing of the synthesis product. Batch electrosynthesis and electrosynthesis with flow synthesis were compared for the quality of the product using Brunauer–Emmett–Teller (BET) surface area, X-ray diffraction (XRD), and scanning electron microscopy (EIS). Batch electrosynthesis in 0.01 M benzene-1,3,5-tricarboxylic acid (H3BTC) solution produced HKUST-1 with BET surface area of 1550 m2/g which was increased further to 1716 m2/g with post-flow-synthesis treatment. The greatest change in surface area after flow processing was observed when using 0.78 M H3BTC, with corresponding surface areas of 481 m2/g and 1531 m2/g. According to SEM and BET results, the product purity improved during the post-flow-synthesis treatment. The proposed method enables continuous flow synthesis of high-quality MOFs with minimal purification steps. Full article
(This article belongs to the Special Issue Synthesis and Applications of Metal-Organic Frameworks (MOFs))
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