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Catalysis by Metal-Organic Frameworks
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Catalysis by Metal-Organic Frameworks

A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Catalytic Materials".

Deadline for manuscript submissions: closed (31 October 2018) | Viewed by 58280

Special Issue Editor

Prof. Dr. Seong Huh

E-Mail Website
Guest Editor
Inorganic Nanomaterials Lab, Department of Chemistry, Hankuk University of Foreign Studies, Seoul, Korea
Interests: multifunctional mesoporous oxide materials; novel mesostructured metals and semiconductors; metal–organic frameworks (MOFs); high efficacy gas storage materials; controllable preparation of shaped nanoparticles; intracellular drug delivery system; supercapacitors; dye-sensitized solar cells (DSSCs); heterogeneous catalysis
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Numerous functional metal-organic frameworks (MOFs) are being assembled from various metal ions and polytopic bridging ligands. These crystalline MOFs tend to form unique topologically interesting networks. Additionally, MOFs often exhibit robust frameworks with high surfaces and large pore volumes. The confined spaces of MOFs are ideal platforms for a range of new heterogeneous catalytic systems with high selectivity and recyclability. The incorporation of catalytically-active functional moieties into the bridging ligands or generation of open-metal sites are good methods for the preparation of novel catalysts. A simple encapsulation of catalytically-active nanoparticles inside MOF channels is also promising strategy to prepare active catalysts. The scope of this special issue covers all areas of MOF-based catalytic systems.

Prof. Dr. Seong Huh
Guest Editor

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Keywords

  • Metal-organic frameworks
  • Heterogeneous catalysis
  • Recyclable catalysts
  • Catalytic organic transformations

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Published Papers (9 papers)

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Research

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12 pages, 4917 KiB  
Article
Thermal Stability and Potential Cycling Durability of Nitrogen-Doped Graphene Modified by Metal-Organic Framework for Oxygen Reduction Reactions
by Harsimranjit Singh, Shiqiang Zhuang, Bharath Babu Nunna and Eon Soo Lee
Catalysts 2018, 8(12), 607; https://doi.org/10.3390/catal8120607 - 3 Dec 2018
Cited by 22 | Viewed by 5352
Abstract
Here we report a nitrogen-doped graphene modified metal-organic framework (N-G/MOF) catalyst, a promising metal-free electrocatalyst exhibiting the potential to replace the noble metal catalyst from the electrochemical systems; such as fuel cells and metal-air batteries. The catalyst was synthesized with a planetary ball [...] Read more.
Here we report a nitrogen-doped graphene modified metal-organic framework (N-G/MOF) catalyst, a promising metal-free electrocatalyst exhibiting the potential to replace the noble metal catalyst from the electrochemical systems; such as fuel cells and metal-air batteries. The catalyst was synthesized with a planetary ball milling method, in which the precursors nitrogen-functionalized graphene (N-G) and ZIF-8 are ground at an optimized grinding speed and time. The N-G/MOF catalyst not only inherited large surface area from the ZIF-8 structure, but also had chemical interactions, resulting in an improved Oxygen Reduction Reaction (ORR) electrocatalyst. Thermogravimetric Analysis (TGA) curves revealed that the N-G/MOF catalyst still had some unreacted ZIF-8 particles, and the high catalytic activity of N-G particles decreased the decomposition temperature of ZIF-8 in the N-G/MOF catalyst. Also, we present the durability study of the N-G/MOF catalyst under a saturated nitrogen and oxygen environment in alkaline medium. Remarkably, the catalyst showed no change in the performance after 2000 cycles in the N2 environment, exhibiting strong resistance to the corrosion. In the O2 saturated electrolyte, the performance loss at lower overpotentials was as low compared to higher overpotentials. It is expected that the catalyst degradation mechanism during the potential cycling is due to the oxidative attack of the ORR intermediates. Full article
(This article belongs to the Special Issue Catalysis by Metal-Organic Frameworks)
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19 pages, 12118 KiB  
Article
Photoreduction of Carbon Dioxide to Methanol over Copper Based Zeolitic Imidazolate Framework-8: A New Generation Photocatalyst
by Sonam Goyal, Maizatul Shima Shaharun, Chong Fai Kait, Bawadi Abdullah and Mariam Ameen
Catalysts 2018, 8(12), 581; https://doi.org/10.3390/catal8120581 - 25 Nov 2018
Cited by 45 | Viewed by 7640
Abstract
The efficient reduction of CO2 into valuable products such as methanol, over metal-organic frameworks (MOFs) based catalyst, has received much attention. The photocatalytic reduction is considered the most economical method due to the utilization of solar energy. In this study, Copper (II)/Zeolitic [...] Read more.
The efficient reduction of CO2 into valuable products such as methanol, over metal-organic frameworks (MOFs) based catalyst, has received much attention. The photocatalytic reduction is considered the most economical method due to the utilization of solar energy. In this study, Copper (II)/Zeolitic Imidazolate Framework-8 (Cu/ZIF-8) catalysts were synthesized via a hydrothermal method for photocatalytic reduction of CO2 to methanol. The synthesized catalysts were characterized by X-ray Photoelectron Spectroscopy (XPS), Field Emission Scanning Electron Microscopy (FESEM) coupled with Energy Dispersive X-ray (EDX), Ultraviolet-visible (UV-vis) spectroscopy, and X-Ray Diffraction (XRD). The host ZIF-8, treated with 2 mmol copper prepared in 2M ammonium hydroxide solution showed the highest photocatalytic activity. The crystal structures of ZIF-8 and 2Cu/ZIF-8N2 catalysts were observed as cubic and orthorhombic, respectively and the XPS analysis confirmed the deposition of Cu (II) ions over ZIF-8 surface among all the prepared catalysts. The orthorhombic structure, nano-sized crystals, morphology and Cu loading of the 2Cu/ZIF-8N2 catalyst were the core factors to influence the photocatalytic activity. The yield of Methanol was found to be 35.82 µmol/L·g after 6 h of irradiations on 2Cu/ZIF-8N2 catalyst in the wavelength range between 530–580 nm. The copper-based ZIF-8 catalyst has proven as an alternative approach for the economical photocatalytic reduction of CO2 to CH3OH. Full article
(This article belongs to the Special Issue Catalysis by Metal-Organic Frameworks)
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11 pages, 2276 KiB  
Article
Three Component Controls in Pillared Metal-Organic Frameworks for Catalytic Carbon Dioxide Fixation
by Jinmi Noh, Dasom Kim, Jihyun Lee, Minyoung Yoon, Myung Hwan Park, Kang Mun Lee, Youngjo Kim and Min Kim
Catalysts 2018, 8(11), 565; https://doi.org/10.3390/catal8110565 - 20 Nov 2018
Cited by 5 | Viewed by 5777
Abstract
Three components of pillared metal-organic frameworks (MOFs, three components = metal ion, carboxylic acid ligand, and N-chelating ligand) were controlled for CO2 cycloaddition catalysts to synthesize organic cyclic carbonates. Among the divalent metals, Zn2+ showed the best catalytic activity, and [...] Read more.
Three components of pillared metal-organic frameworks (MOFs, three components = metal ion, carboxylic acid ligand, and N-chelating ligand) were controlled for CO2 cycloaddition catalysts to synthesize organic cyclic carbonates. Among the divalent metals, Zn2+ showed the best catalytic activity, and in DABCO (1,4-diazabicyclo[2.2.2]octane)-based MOFs, hydroxy-functionalized DMOF-OH was the most efficient MOF for CO2 cycloaddition. For the BPY (4,4’-bipyridyl)-type MOFs, all five prepared BMOFs (BPY MOFs) showed similar and good conversions for CO2 cycloaddition. Finally, this pillared MOF could be recycled up to three times without activity and crystallinity loss. Full article
(This article belongs to the Special Issue Catalysis by Metal-Organic Frameworks)
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10 pages, 3110 KiB  
Article
HKUST-1 Supported on Zirconium Phosphate as an Efficient Catalyst for Solvent Free Oxidation of Cyclohexene: DFT Study
by Razia Aman, Abraham Clearfield, Mohammad Sadiq and Zahid Ali
Catalysts 2018, 8(11), 546; https://doi.org/10.3390/catal8110546 - 15 Nov 2018
Cited by 4 | Viewed by 4558
Abstract
Layer by layer metal-organic framework (MOF) supported on zirconium phosphate (ZrP) was synthesized at very mild conditions and used for the liquid phase oxidation of cyclohexene in solvent free condition in the presence of molecular oxygen. The MOF-ZrP was characterized by X-ray diffractometer [...] Read more.
Layer by layer metal-organic framework (MOF) supported on zirconium phosphate (ZrP) was synthesized at very mild conditions and used for the liquid phase oxidation of cyclohexene in solvent free condition in the presence of molecular oxygen. The MOF-ZrP was characterized by X-ray diffractometer (XRD), scanning electron microscope (SEM), thermal gravimetric analyzer (TGA), Fourier-transform infrared spectrometer (FT-IR) and Brunauer-Emmett-Teller (BET) surface area analyzer. The characterization shows a smooth morphology of MOF-ZrP with good stability under 200 °C having surface area 285 m2/g. The catalytic activity of the MOF-ZrP revealed that increase of layers of MOF on ZrP enhances conversion, as well as selectivity of oxidation of cyclohexene. DFT studies were used to explore the structure and electron properties of HKUST-1 (Hong Kong University of Science and Technology), which is a clue for the catalytic behavior of the catalyst. Full article
(This article belongs to the Special Issue Catalysis by Metal-Organic Frameworks)
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8 pages, 2393 KiB  
Communication
Synthesis of Stable Hierarchical MIL-101(Cr) with Enhanced Catalytic Activity in the Oxidation of Indene
by Tian Zhao, Ming Dong, Ling Yang and Yuejun Liu
Catalysts 2018, 8(9), 394; https://doi.org/10.3390/catal8090394 - 13 Sep 2018
Cited by 28 | Viewed by 4972
Abstract
Nowadays, the controllable synthesis of stable hierarchical metal–organic frameworks (MOFs) is very important for practical applications, especially in catalysis. Herein, a well-known chromium–benzenedicarboxylate metal–organic framework, MIL-101(Cr), with a stable hierarchical structure, was produced by using phenylphosphonic acid (PPOA) as a modulator via the [...] Read more.
Nowadays, the controllable synthesis of stable hierarchical metal–organic frameworks (MOFs) is very important for practical applications, especially in catalysis. Herein, a well-known chromium–benzenedicarboxylate metal–organic framework, MIL-101(Cr), with a stable hierarchical structure, was produced by using phenylphosphonic acid (PPOA) as a modulator via the hydrothermal method. The presence of phenylphosphonic acid could create structural defects and generate larger mesopores. The synthesized hierarchical MIL-101(Cr) possesses relatively good porosity, and the larger mesopores had widths of 4–10 nm. The hierarchical MIL-101(Cr) showed significant improvement for catalytic activity in the oxidation of indene. Further, the presence of a hierarchical structure could largely enhance large dye molecule uptake properties by impregnating. Full article
(This article belongs to the Special Issue Catalysis by Metal-Organic Frameworks)
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9 pages, 1408 KiB  
Communication
A Zn-MOF-Catalyzed Terpolymerization of Propylene Oxide, CO2, and β-butyrolactone
by Sudakar Padmanaban, Sivanesan Dharmalingam and Sungho Yoon
Catalysts 2018, 8(9), 393; https://doi.org/10.3390/catal8090393 - 13 Sep 2018
Cited by 13 | Viewed by 5160
Abstract
The terpolymerization of propylene oxide (PO), CO2, and a lactone is one of the prominent sustainable procedures for synthesizing thermoplastic materials at an industrial scale. Herein, the one-pot terpolymerization of PO, CO2, and β-butyrolactone (BBL) was achieved for the [...] Read more.
The terpolymerization of propylene oxide (PO), CO2, and a lactone is one of the prominent sustainable procedures for synthesizing thermoplastic materials at an industrial scale. Herein, the one-pot terpolymerization of PO, CO2, and β-butyrolactone (BBL) was achieved for the first time using a heterogeneous nano-sized catalyst: zinc glutarate (ZnGA-20). The reactivity of both PO and BBL increased with the CO2 pressure, and the polyester content of the terpolymer poly (carbonate-co-ester) could be tuned by controlling the infeed ratio of PO to BBL. When the polyester content increased, the thermal stability of the polymers increased, whereas the glass transition temperature (Tg) decreased. Full article
(This article belongs to the Special Issue Catalysis by Metal-Organic Frameworks)
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10 pages, 5949 KiB  
Article
Interface-Active Metal Organic Frameworks for Knoevenagel Condensations in Water
by Yanmei Zhang, Xiang Zhang, Rixia Bai, Xiyan Hou and Jun Li
Catalysts 2018, 8(8), 315; https://doi.org/10.3390/catal8080315 - 1 Aug 2018
Cited by 13 | Viewed by 4143
Abstract
It is desirable but challenging to locate solid catalysts at the oil-water interface to stabilize “Pickering emulsions”, which is one of the promising ways to develop efficient green chemical processes. Herein, water-stable metal organic framework ZIF-8 without any chemical modification was demonstrated to [...] Read more.
It is desirable but challenging to locate solid catalysts at the oil-water interface to stabilize “Pickering emulsions”, which is one of the promising ways to develop efficient green chemical processes. Herein, water-stable metal organic framework ZIF-8 without any chemical modification was demonstrated to be an interface-active catalyst for Knoevenagel condensation in a biphasic system. Pickering emulsion formed under the reaction conditions due to its amphiphilic property, which was beneficial to the mass transfer and led to high catalytic performance. Moreover, it can be repeatedly applied for Knoevenagel condensation for at least six successive cycles without losing its catalytic activity and framework integrity. Full article
(This article belongs to the Special Issue Catalysis by Metal-Organic Frameworks)
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Review

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20 pages, 34316 KiB  
Review
Direct Catalytic Conversion of CO2 to Cyclic Organic Carbonates under Mild Reaction Conditions by Metal—Organic Frameworks
by Seong Huh
Catalysts 2019, 9(1), 34; https://doi.org/10.3390/catal9010034 - 2 Jan 2019
Cited by 49 | Viewed by 8139
Abstract
The reduction of the representative greenhouse gas, carbon dioxide (CO2), is significantly an important theme for the current research in the modern chemical world. For the last two decades, the development of new metal-organic framework (MOF) systems with highly selective capture [...] Read more.
The reduction of the representative greenhouse gas, carbon dioxide (CO2), is significantly an important theme for the current research in the modern chemical world. For the last two decades, the development of new metal-organic framework (MOF) systems with highly selective capture of CO2, in the presence of other competing gaseous molecules, has flourished to capture or separate CO2 for environmental protection. Nonetheless, the ultimate resolution to lessen the atmospheric CO2 concentration may be in the chemical or electrochemical conversion of CO2 to other compounds. In this context, the catalytic cycloaddition reaction of CO2 into organic epoxides to produce cyclic carbonates is a more attractive method. MOFs are being proven as efficient heterogeneous catalytic systems for this important reaction. In this review, we collected very recent progress in MOF-based catalytic systems, fully operable under very mild reaction conditions (room temperature and 1 atm CO2). Full article
(This article belongs to the Special Issue Catalysis by Metal-Organic Frameworks)
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28 pages, 8552 KiB  
Review
Recent Progress in Asymmetric Catalysis and Chromatographic Separation by Chiral Metal–Organic Frameworks
by Suchandra Bhattacharjee, Muhammad Imran Khan, Xiaofang Li, Qi-Long Zhu and Xin-Tao Wu
Catalysts 2018, 8(3), 120; https://doi.org/10.3390/catal8030120 - 19 Mar 2018
Cited by 76 | Viewed by 11079
Abstract
Metal–organic frameworks (MOFs), as a new class of porous solid materials, have emerged and their study has established itself very quickly into a productive research field. This short review recaps the recent advancement of chiral MOFs. Here, we present simple, well-ordered instances to [...] Read more.
Metal–organic frameworks (MOFs), as a new class of porous solid materials, have emerged and their study has established itself very quickly into a productive research field. This short review recaps the recent advancement of chiral MOFs. Here, we present simple, well-ordered instances to classify the mode of synthesis of chiral MOFs, and later demonstrate the potential applications of chiral MOFs in heterogeneous asymmetric catalysis and enantioselective separation. The asymmetric catalysis sections are subdivided based on the types of reactions that have been successfully carried out recently by chiral MOFs. In the part on enantioselective separation, we present the potentiality of chiral MOFs as a stationary phase for high-performance liquid chromatography (HPLC) and high-resolution gas chromatography (GC) by considering fruitful examples from current research work. We anticipate that this review will provide interest to researchers to design new homochiral MOFs with even greater complexity and effort to execute their potential functions in several fields, such as asymmetric catalysis, enantiomer separation, and chiral recognition. Full article
(This article belongs to the Special Issue Catalysis by Metal-Organic Frameworks)
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