Polymer in MOF Nanospace: from Controlled Chain Assembly to New Functional Materials

Ouay, Benjamin Le; Uemura, Takashi

doi:10.1002/ijch.201800074

Cited by 20 publications

(15 citation statements)

References 129 publications

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“…It should be noted that integrating polymers and MOFs is an emerging topic in the field. 39,40 Nonetheless, to date, there are no reports showing methods that are capable of maintaining the structural integrity of mesoporous MOFs during activation. However, there has been some recent works in the literature that demonstrate that the insertion of polymer guests can enhance mechanical stability and decrease flexibility in microporous MOFs.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Inspired by previous work on M 2 (NDISA), we hypothesized that inserting polymer guests into this material could pin the mesopore open and also enhance the mechanical stability of the framework, maintaining porosity even upon harsh activation conditions. It should be noted that integrating polymers and MOFs is an emerging topic in the field. , Nonetheless, to date, there are no reports showing methods that are capable of maintaining the structural integrity of mesoporous MOFs during activation. However, there has been some recent works in the literature that demonstrate that the insertion of polymer guests can enhance mechanical stability and decrease flexibility in microporous MOFs. , …”

Section: Introductionmentioning

confidence: 99%

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Preserving Porosity of Mesoporous Metal–Organic Frameworks through the Introduction of Polymer Guests

Yang

Jawahery

et al. 2019

J. Am. Chem. Soc.

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High internal surface areas, an asset that is highly sought after in material design, has brought metal−organic frameworks (MOFs) to the forefront of materials research. In fact, a major focus in the field is on creating innovative ways to maximize MOF surface areas. Despite this, large-pore MOFs, particularly those with mesopores, continue to face problems with pore collapse upon activation. Herein, we demonstrate an easy method to inhibit this problem via the introduction of small quantities of polymer. For several mesoporous, isostructural MOFs, known as M 2 (NDISA) (where M = Ni 2+ , Co 2+ , Mg 2+ , or Zn 2+ ), the accessible surface areas are increased dramatically, from 5 to 50 times, as the polymer effectively pins the MOFs open. Postpolymerization, the high surface areas and crystallinity are now readily maintained after heating the materials to 150 °C under vacuum. These activation conditions, which could not previously be attained due to pore collapse, also provide accessibility to high densities of open metal coordination sites. Molecular simulations are used to provide insight into the origin of instability of the M 2 (NDISA) series and to propose a potential mechanism for how the polymers immobilize the linkers, improving framework stability. Last, we demonstrate that the resulting MOF−polymer composites, referred to as M 2 (NDISA)-PDA, offer a perfect platform for the appendage/immobilization of small nanocrystals inside rendering high-performance catalysts. After decorating one of the composites with Pd (average size: 2 nm) nanocrystals, the material shows outstanding catalytic activity for Suzuki−Miyaura cross-coupling reactions.

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Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Preserving Porosity of Mesoporous Metal–Organic Frameworks through the Introduction of Polymer Guests

Yang

Jawahery

et al. 2019

J. Am. Chem. Soc.

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Section: Conductive Behavior In Metal‐organic Framework Filmsmentioning

confidence: 99%

“…In addition, polymerization in a confined space can yield polymers with controllable structures, which is essential for adjusting and enhancing the function of hybrid materials. [113,114] In 2018, Lu et al introduced aniline (An) into Zr-MOFs using this strategy and formed a Zr-MOF/PAn/(styrene sulfonate) (PSS) composite film by APS (ammonium persulfate)-catalyzed oxidative polymerization inside the pores. [115] During the doping process, the polystyrene sulfonic acid was used as the dopant, and polyaniline (PAn) chains interpenetrated into the whole Zr-MOFs, enhancing the crystallinity of PAn and increasing the conductivity of the MOF film (Figure 11a).…”

Section: Introduction Of a Conductive Polymermentioning

confidence: 99%

Recent Progress on Conductive Metal‐Organic Framework Films

Wang

Sun

et al. 2021

Adv Materials Inter

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Because of their outstanding structural, chemical, and functional diversity, metal‐organic frameworks (MOFs) have brought about worldwide interest over the last 2 decades, which have been utilized in a wide range of applications in the fields of gas separation, storage, catalysis, and drug delivery. However, among these applications, MOFs are almost used in the form of powder. Due to their fragility and difficulty in preparing large‐area thin film materials, the study of MOF films and their electronic properties is a challenging problem in the research of MOFs. Owing to the low‐energy charge transport mode, most MOF films are essentially insulating, which largely limits their applications in fields where electronic charge transport takes place, such as electronics or electrochemistry. So, the introduction of conductivity into the MOF films opens new avenues for their applications in electrochemical sensing, supercapacitors, batteries, electrocatalysis, and electronic devices and makes the research on and with MOF films very active. Herein, the latest progress of conductive MOF films, including the preparation of MOF films, the design and adjustment strategies for constructing intrinsic and doping conductive MOF films, and their applications are reviewed. In addition, the numerous challenges of conductive MOF films are also elaborated.

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“…The nanopores of MOFs can destroy the natural winding of polymer chains and bring new characteristics. [63] For example, polymerization changes dramatically due to constraints at nanochannel scale, and the engineering of the main structure (sequence, tactical or branching) can be easily achieved. Due to restriction and extension of chain, the physical/chemical properties can be greatly improved relative to the bulk ploymers.…”

Section: Polymer@mofsmentioning

confidence: 99%

Nanospace Engineering of Metal‐Organic Frameworks for Heterogeneous Catalysis

Wang

Yang

et al. 2021

ChemNanoMat

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The structural advantages of metal-organic frameworks (MOFs) can facilitate wide applications in the field of catalysis, including oxidation, hydrogenation, acetalization, transesterification, catalytic cracking, and so on. The efficiency of catalysis is closely related to the synergy between active center, auxiliary center, and microenvironment. Researchers can customize MOFs according to the needs of catalytic reactions, and many strategies were established for boosting catalytic performance. In this review, we aim to summarize and illustrate recent progress in the nanospace engineering of MOFs. Generally, MOFs were engineered mainly from the following aspects: 1) Regulation of pore size, including micropores, mesopores, and macropores. 2) Engineering of encapsulated active species, such as metal nanoparticles, quantum dots, polyoxometalates, enzymes, etc. 3) Engineering of MOFs morphology from zero dimension to three-dimension. 4) Controllable integration of MOFs with multi-strategies. 5) Construction of multivariate MOFs via introducing multiple or mixed organic functional groups into the existing framework. Besides, for further low cost and practical applications, challenges for MOFs as green and sustainable catalysts are also discussed.

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Polymer in MOF Nanospace: from Controlled Chain Assembly to New Functional Materials

Cited by 20 publications

References 129 publications

Preserving Porosity of Mesoporous Metal–Organic Frameworks through the Introduction of Polymer Guests

Preserving Porosity of Mesoporous Metal–Organic Frameworks through the Introduction of Polymer Guests

Recent Progress on Conductive Metal‐Organic Framework Films

Nanospace Engineering of Metal‐Organic Frameworks for Heterogeneous Catalysis

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