Metal-Organic Framework Materials as Catalysts

A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Catalysis in Organic and Polymer Chemistry".

Deadline for manuscript submissions: closed (15 July 2023) | Viewed by 18001

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Guest Editor
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan, China
Interests: porous materials; MOF design; MOF synthesis; MOF functionalization and composite; MOF-derived materials; catalysis; gas adsorption; gas separation; carbon dioxide utilization
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Dear Colleagues,

Since the 1990s, selective heterogeneous catalytic organic transformations have been one of the most promising applications of microporous MOFs. Importantly, the high porosity of MOFs allows for their mass transportation and facilitates their interaction with substrates. More than 3,000 MOFs have been made so far, while more are in development, and they represent one of modern science’s most dynamic fields of research.

Heterogeneous catalysis plays an increasingly crucial role in chemical manufacturing, often leading to a major reduction in waste. The use of MOFs as heterogeneous catalysts has helped enormously in the last two decades as they are an eco-friendly alternative to homogeneous catalysis. MOFs have been employed as solid catalysts for a variety of organic transformations, including alkylation, acylation, oxidation, epoxidation, hydrogenation, condensation, esterification, metathesis, and Diels–Alder reactions, etc. The separation of the reaction products, the reusability of catalysts, and fewer leaching problems make MOFs superior as active heterogeneous catalysts.

The goal of this Special Issue's is to showcase the frontiers of academic research into catalysis with MOFs and their derivates. MOF catalysis can be based on the active sites in a framework, i.e., metal nodes and organic linkers and the loading of nano-metals and metal oxides. Moreover, the encapsulation of catalytically active species, post-chemical modifications of MOFs, multifunctional MOFs, mixed linker MOFs, and asymmetric MOFs for catalyzed organic transformations are all of interest for this Special Issue.

This Special Issue deals with all aspects of MOFs related to heterogeneous catalysis, catalyst synthesis, and characterizations of their various applications in molecular transformations. Both original research and comprehensive review papers and perspectives contributing to the field are welcome.

The primary area of study can, however, span a broad research area, which focusses on catalysis in combination with MOFs:

Prof. Dr. Francis Verpoort
Dr. Somboon Chaemchuen
Guest Editors

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Keywords

  • MOFs in catalysis for chemicals
  • MOFs in electrocatalysis
  • MOFs in photocatalysis
  • MOF derivates in catalysis
  • MOF catalysts for polymerizations
  • MOFs in enantioselective catalysis
  • MOF derivatives in catalysis
  • Further areas for development and new perspectives

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Published Papers (8 papers)

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Research

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14 pages, 4294 KiB  
Article
Green Approach for Synthesizing Copper-Containing ZIFs as Efficient Catalysts for Click Chemistry
by Alireza Pourvahabi Anbari, Shima Rahmdel Delcheh, Philippe M. Heynderickx, Somboon Chaemcheun, Serge Zhuiykov and Francis Verpoort
Catalysts 2023, 13(6), 1003; https://doi.org/10.3390/catal13061003 - 14 Jun 2023
Cited by 2 | Viewed by 1497
Abstract
ZIF-8 and ZIF-67 containing various percentages of copper were successfully synthesized through a green in-situ thermal (IST) approach based on 2-methylimidazole (2-MIM) as the organic linker. The IST method has several advantages over previously reported studies, including solvent and additive-free reaction conditions, a [...] Read more.
ZIF-8 and ZIF-67 containing various percentages of copper were successfully synthesized through a green in-situ thermal (IST) approach based on 2-methylimidazole (2-MIM) as the organic linker. The IST method has several advantages over previously reported studies, including solvent and additive-free reaction conditions, a mild reaction temperature, a single-step procedure, no activation requirements, and the use of the smallest precursor ratio (M/L). The high catalytic performance of Cu/ZIF-8 and Cu/ZIF-67 in click chemistry is attributed to their high specific surface area, excellent porosity, and structural stability. To achieve these features, a range of parameters—such as time, temperature, gas atmosphere, and precursor ratio—were optimized. Several characterization methods were used to confirm the features of the produced catalysts. Overall, the synthesis strategy for achieving the targeted ZIFs with unique features is “green” and does not require further activation or treatment to eliminate side products. This method has great potential for manufacturing metal-organic frameworks on a large scale. Moreover, water was used as a solvent during the click reaction, resulting in high yields and making this an attractive, green, and eco-friendly procedure. Full article
(This article belongs to the Special Issue Metal-Organic Framework Materials as Catalysts)
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11 pages, 3398 KiB  
Article
Metallic–Organic Cages (MOCs) with Heterometallic Character: Flexibility-Enhancing MOFs
by Sergio Posada-Pérez, Jordi Poater, Naeimeh Bahri-Laleh and Albert Poater
Catalysts 2023, 13(2), 317; https://doi.org/10.3390/catal13020317 - 1 Feb 2023
Viewed by 1614
Abstract
The dichotomy between metal–organic frameworks (MOFs) and metal–organic cages (MOCs) opens up the research spectrum of two fields which, despite having similarities, both have their advantages and disadvantages. Due to the fact that they have cavities inside, they also have applicability in the [...] Read more.
The dichotomy between metal–organic frameworks (MOFs) and metal–organic cages (MOCs) opens up the research spectrum of two fields which, despite having similarities, both have their advantages and disadvantages. Due to the fact that they have cavities inside, they also have applicability in the porosity sector. Bloch and coworkers within this evolution from MOFs to MOCs manage to describe a MOC with a structure of Cu2 paddlewheel Cu4L4 (L = bis(pyrazolyl)methane) with high precision thanks to crystallographic analyses of X-ray diffraction and also SEM-EDX. Then, also at the same level of concreteness, they were able to find the self-assembly of Pd(II)Cl2 moieties on the available nitrogen donor atoms leading to a [Cu4(L(PdCl2))4] structure. Here, calculations of the DFT density functional allow us to reach an unusual precision given the magnitude and structural complexity, explaining how a pyrazole ring of each bis(pyprazolyl)methane ligand must rotate from an anti to a syn conformation, and a truncation of the MOC structure allows us to elucidate, in the absence of the MOC constraint and its packing in the crystal, that the rotation is almost barrierless, as well as also explain the relative stability of the different conformations, with the anti being the most stable conformation. Characterization calculations with Mayer bond orders (MBO) and noncovalent interaction (NCI) plots discern what is important in the interaction of this type of cage with PdCl2 moieties, also CuCl2 by analogy, as well as simple molecules of water, since the complex is stable in this solvent. However, the L ligand is proved to not have the ability to stabilize an H2O molecule. Full article
(This article belongs to the Special Issue Metal-Organic Framework Materials as Catalysts)
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12 pages, 4748 KiB  
Article
Synthesis of Phenol-Tagged Ruthenium Alkylidene Olefin Metathesis Catalysts for Robust Immobilisation Inside Metal–Organic Framework Support
by Maryana Nadirova, Joel Cejas-Sánchez, Rosa María Sebastián, Marcin Wiszniewski, Michał J. Chmielewski, Anna Kajetanowicz and Karol Grela
Catalysts 2023, 13(2), 297; https://doi.org/10.3390/catal13020297 - 28 Jan 2023
Cited by 1 | Viewed by 2702
Abstract
Two new unsymmetrical N-heterocyclic carbene ligand (uNHC)-based ruthenium complexes featuring phenolic OH function were obtained and fully characterised. The more active one was then immobilised on the metal–organic framework (MOF) solid support (Al)MIL-101-NH2. The catalytic activity of such a heterogeneous system [...] Read more.
Two new unsymmetrical N-heterocyclic carbene ligand (uNHC)-based ruthenium complexes featuring phenolic OH function were obtained and fully characterised. The more active one was then immobilised on the metal–organic framework (MOF) solid support (Al)MIL-101-NH2. The catalytic activity of such a heterogeneous system was tested, showing that, while the heterogeneous catalyst is less active than the corresponding homogeneous catalyst in solution, it can catalyse selected olefin metathesis reactions, serving as the proof-of-concept for the immobilisation of catalytically active complexes in MOFs using a phenolic tag. Full article
(This article belongs to the Special Issue Metal-Organic Framework Materials as Catalysts)
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10 pages, 2264 KiB  
Article
MOF-Based G−Quadruplex/Hemin DNAzymes for Cascade Reaction
by Ying Zhang, Junya Liao and Hao Liang
Catalysts 2023, 13(1), 81; https://doi.org/10.3390/catal13010081 - 30 Dec 2022
Cited by 1 | Viewed by 1671
Abstract
DNA-based biomimetic enzymes have attracted extensive attention due to their unique structure and stability compared to natural enzymes. Meanwhile, the specific sequences of DNA itself also have a catalytic effect. Herein, we first designed three guanine-rich DNA sequences numbered c−Myc3c, PG4TC, and TTT [...] Read more.
DNA-based biomimetic enzymes have attracted extensive attention due to their unique structure and stability compared to natural enzymes. Meanwhile, the specific sequences of DNA itself also have a catalytic effect. Herein, we first designed three guanine-rich DNA sequences numbered c−Myc3c, PG4TC, and TTT to construct g−quadruplex/hemin DNAzymes. Then, the g−quadruplex/hemin DNAzymes with the best activity were selected by a comprehensive examination of activity, degradation rate, and affinity. Subsequently, the stability and reusability of UiO66−DNAzymes were investigated using UiO66 as the carrier to immobilize DNAzymes. The results showed that UiO66−DNAzymes had excellent reusability and stability. Finally, UiO66−DNAzymes were successfully used for glucose detection by cascading with glucose oxidase (GOx) with a detection limit of 0.62 μM. The constructed glucose sensor had a good specificity, which is of great significance for developing a novel, accurate, fast, and economical glucose detection sensor. Full article
(This article belongs to the Special Issue Metal-Organic Framework Materials as Catalysts)
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15 pages, 4733 KiB  
Article
Tuning the Hydrophobicity and Lewis Acidity of UiO-66-NO2 with Decanoic Acid as Modulator to Optimise Conversion of Glucose to 5-Hydroxymethylfurfural
by Yongzhao Zhang, Baiwen Zhao, Satarupa Das, Volkan Degirmenci and Richard I. Walton
Catalysts 2022, 12(12), 1502; https://doi.org/10.3390/catal12121502 - 23 Nov 2022
Cited by 5 | Viewed by 1539
Abstract
Glucose conversion to 5-hydroxymethylfurfural (HMF) is important to the success of a biorefinery. Herein, metal–organic frameworks (MOFs) with the UiO-66 structure were synthesised with decanoic acid as the modulator and used as the catalyst to optimise HMF yield. PXRD, FTIR, and TGA/DSC techniques [...] Read more.
Glucose conversion to 5-hydroxymethylfurfural (HMF) is important to the success of a biorefinery. Herein, metal–organic frameworks (MOFs) with the UiO-66 structure were synthesised with decanoic acid as the modulator and used as the catalyst to optimise HMF yield. PXRD, FTIR, and TGA/DSC techniques were applied to characterise the materials. The analysis results show that the materials assembled from the ligand 2-nitroterephthalic acid and hexameric Zr-oxo clusters contain decanoic acid chemically bound in the framework that influences porosity, Lewis acidity, and hydrophobicity. The materials exhibit excellent catalytic performance for HMF production from glucose in DMSO as solvent, attributed to their abundant defects and high hydrophobicity due to the addition of the decanoic acid modulator. Influences of catalyst dosages, reaction duration, and temperature were comprehensively investigated, leading to 98.1% conversion of glucose and 54.5% HMF yield under optimised reaction conditions. The catalytic conversion shows some deterioration after four cycles, yet the reaction selectivity displays no significant decline. Full article
(This article belongs to the Special Issue Metal-Organic Framework Materials as Catalysts)
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22 pages, 5559 KiB  
Article
Microwave-Assisted Biodiesel Production Using UiO-66 MOF Derived Nanocatalyst: Process Optimization Using Response Surface Methodology
by Shiva Prasad Gouda, Jasha Momo H. Anal, Puneet Kumar, Amarajothi Dhakshinamoorthy, Umer Rashid and Samuel Lalthazuala Rokhum
Catalysts 2022, 12(11), 1312; https://doi.org/10.3390/catal12111312 - 26 Oct 2022
Cited by 14 | Viewed by 2272
Abstract
The present work is on the transesterification of soybean oil to biodiesel under microwave irradiation using a biomass and MOF−derived CaO−ZrO2 heterogeneous catalyst. The optimisation of different parameters was processed by adopting a central composite design for a response−surface methodology (RSM). The [...] Read more.
The present work is on the transesterification of soybean oil to biodiesel under microwave irradiation using a biomass and MOF−derived CaO−ZrO2 heterogeneous catalyst. The optimisation of different parameters was processed by adopting a central composite design for a response−surface methodology (RSM). The experimental data were fitted to a quadratic equation employing multiple regressions and investigated by analysis of variance (ANOVA). The catalyst was exhaustively characterised by XRD, TGA, FTIR BET, SEM, TEM, CO2 TPD and XPS. In addition, the synthesized biodiesel was characterized by 1H and 13C NMR, GCMS. The physicochemical properties of the biodiesel were also reported and compared with the ASTM standards. The maximum yield that was obtained after optimization using RSM was 97.22 ± 0.4% with reaction time of 66.2 min, at reaction temperature of 73.2 °C, catalyst loading of 6.5 wt.%, and methanol−to−oil ratio of 9.7 wt.%. Full article
(This article belongs to the Special Issue Metal-Organic Framework Materials as Catalysts)
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12 pages, 2156 KiB  
Article
Two-Dimensional Zeolitic Imidazolate Framework ZIF-L: A Promising Catalyst for Polymerization
by M. Abdur Rahaman, Bibimaryam Mousavi, Farah Naz and Francis Verpoort
Catalysts 2022, 12(5), 521; https://doi.org/10.3390/catal12050521 - 6 May 2022
Cited by 8 | Viewed by 3345
Abstract
Here, for the first time, a 2D and leaf-like zeolitic imidazolate framework (ZIF-L) is reported for the synthesis of ultrahigh molecular weight (UHMW) poly(methyl methacrylate) (PMMA) with Mn up to 1390 kg mol−1. This synthesis method is a one-step process [...] Read more.
Here, for the first time, a 2D and leaf-like zeolitic imidazolate framework (ZIF-L) is reported for the synthesis of ultrahigh molecular weight (UHMW) poly(methyl methacrylate) (PMMA) with Mn up to 1390 kg mol−1. This synthesis method is a one-step process without any co-catalyst in a solvent-free medium. SEM, PXRD, FT-IR, TGA, and nitrogen sorption measurements confirmed the 2D and leaf-like structure of ZIF-L. The results of PXRD, SEM, TGA demonstrate that the catalyst ZIF-L is remarkably stable even after a long-time polymerization reaction. Zwitterionic Lewis pair polymerization (LPP) has been proposed for the catalytic performance of ZIF-L on methyl methacrylate (MMA) polymerization. This MMA polymerization is consistent with a living system, where ZIF-L could reinitiate the polymerization and propagates the process by gradually growing the polymer chains. Full article
(This article belongs to the Special Issue Metal-Organic Framework Materials as Catalysts)
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Review

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34 pages, 30049 KiB  
Review
Opportunities from Metal Organic Frameworks to Develop Porous Carbons Catalysts Involved in Fine Chemical Synthesis
by Elena Pérez-Mayoral, Marina Godino-Ojer, Ines Matos and Maria Bernardo
Catalysts 2023, 13(3), 541; https://doi.org/10.3390/catal13030541 - 8 Mar 2023
Cited by 5 | Viewed by 2378
Abstract
In the last decade, MOFs have been proposed as precursors of functional porous carbons with enhanced catalytic performances by comparison with other traditional carbonaceous catalysts. This area is rapidly growing mainly because of the great structural diversity of MOFs offering almost infinite possibilities. [...] Read more.
In the last decade, MOFs have been proposed as precursors of functional porous carbons with enhanced catalytic performances by comparison with other traditional carbonaceous catalysts. This area is rapidly growing mainly because of the great structural diversity of MOFs offering almost infinite possibilities. MOFs can be considered as ideal platforms to prepare porous carbons with highly dispersed metallic species or even single-metal atoms under strictly controlled thermal conditions. This review briefly summarizes synthetic strategies to prepare MOFs and MOF-derived porous carbons. The main focus relies on the application of the MOF-derived porous carbons to fine chemical synthesis. Among the most explored reactions, the oxidation and reduction reactions are highlighted, although some examples of coupling and multicomponent reactions are also presented. However, the application of this type of catalyst in the green synthesis of biologically active heterocyclic compounds through cascade reactions is still a challenge. Full article
(This article belongs to the Special Issue Metal-Organic Framework Materials as Catalysts)
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