Formation of Foam‐like Microstructural Carbon Material by Carbonization of Porous Coordination Polymers through a Ligand‐Assisted Foaming Process

Kongpatpanich, Kanokwan; Horike, Satoshi; Fujiwara, Yu Ichi; Ogiwara, Naoki; Nishihara, Hirotomo; Kitagawa, Susumu

doi:10.1002/chem.201501988

Cited by 14 publications

(10 citation statements)

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“… 5 − 8 Multistep procedures and complex templates are commonly used to fabricate these materials, but few structures with multilevel hierarchy have been formed via facile bottom-up approaches. 3 , 5 Recent work has explored carbonizing metal–organic frameworks (MOFs) 7 − 15 and in a few cases with Ni, Co, Fe, and other catalytically active metals centers (as a part of the MOF’s secondary building unit) has resulted in carbon-fiber assemblies. 16 − 23 Guest incorporation in the open porous MOFs can render the MOFs with tunable chemical composition and additional functionality.…”

Section: Introductionmentioning

confidence: 99%

“…Three-dimensional carbon-based structures with multilevel hierarchy − from low-dimensional nanostructured building blocks (e.g., carbon dots, fullerenes, nanofibers/tubes, and graphene) can greatly exceed the properties of bulk carbon materials in numerous applications, such as lightweight but strong structures and energy storage. − Multistep procedures and complex templates are commonly used to fabricate these materials, but few structures with multilevel hierarchy have been formed via facile bottom-up approaches. , Recent work has explored carbonizing metal–organic frameworks (MOFs) − and in a few cases with Ni, Co, Fe, and other catalytically active metals centers (as a part of the MOF’s secondary building unit) has resulted in carbon-fiber assemblies. − Guest incorporation in the open porous MOFs can render the MOFs with tunable chemical composition and additional functionality. − So far, MOF–guest systems, such as Mo-based polyoxometalate@HKUST-1(Cu), W-based metal-carbonyl@MAF-6(Zn), Ti-oxo clusters@ HKUST-1(Cu), and dicyandiamide/FeCl 3 @MIL-101-NH 2 (Al), have been carbonized to produce advanced electrocatalysts or photocatalysts with desired compositions. However, neither a drastic morphology change nor carbon-based hierarchical structure formation was reported.…”

Section: Introductionmentioning

confidence: 99%

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Bottom-up Formation of Carbon-Based Structures with Multilevel Hierarchy from MOF–Guest Polyhedra

et al. 2018

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Three-dimensional carbon-based structures have proven useful for tailoring material properties in structural mechanical and energy storage applications. One approach to obtain them has been by carbonization of selected metal–organic frameworks (MOFs) with catalytic metals, but this is not applicable to most common MOF structures. Here, we present a strategy to transform common MOFs, by guest inclusions and high-temperature MOF–guest interactions, into complex carbon-based, diatom-like, hierarchical structures (named for the morphological similarities with the naturally existing diatomaceous species). As an example, we introduce metal salt guests into HKUST-1-type MOFs to generate a family of carbon-based nano-diatoms with two to four levels of structural hierarchy. We report control of the morphology by simple changes in the chemistry of the MOF and guest, with implications for the formation mechanisms. We demonstrate that one of these structures has unique advantages as a fast-charging lithium-ion battery anode. The tunability of composition should enable further studies of reaction mechanisms and result in the growth of a myriad of unprecedented carbon-based structures from the enormous variety of currently available MOF–guest candidates.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Bottom-up Formation of Carbon-Based Structures with Multilevel Hierarchy from MOF–Guest Polyhedra

et al. 2018

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“…In situ generated gas outflux can sometimes create additional mesopores and even macropores. [327][328][329] The well-defined periodic arrangement of metal nodes and organic motifs in MOF often leads to a homogeneous distribution of metal or metal oxide nanoparticles in carbon matrix. 320,330 This feature even allows preparation of single atomic metal catalysts and metal-N-C active sites throughout the whole structures, which is useful for various applications.…”

Section: Controlling Morphology Of Metal-organic Framework-derived Carbonmentioning

confidence: 99%

“…This process typically leads to formation of random mesopores in MDCs, yet can be modified to afford foam-like macroporous structures as well. Kitagawa and coworkers 327 reported a ligand-assisted foaming process by using MOFs constructed by Zn 2+ and ligands with nitro group substituents. During carbonization, the nitro group rapidly decomposed/released a large amount of NO2 which act as foaming agents to create hierarchically porous carbon networks.…”

Section: Carbonization Mechanismmentioning

confidence: 99%

Controlling the morphology of metal–organic frameworks and porous carbon materials: metal oxides as primary architecture-directing agents

et al. 2020

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“…Aerogels are generally used as the reinforcements for composites due to their stable self‐supporting networks, good continuity, and abundant porosity . Unlike traditional nanoparticle fillers, aerogel fillers enable better control of the distribution of the reinforcement in the matrix material, e.g., polymers .…”

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confidence: 99%

A Directional Strain Sensor Based on Anisotropic Microhoneycomb Cellulose Nanofiber‐Carbon Nanotube Hybrid Aerogels Prepared by Unidirectional Freeze Drying

Wang

Pan

et al. 2019

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Aerogels are generally used as the reinforcements for composites due to their stable self-supporting networks, good continuity, and abundant porosity. [1][2][3][4][5][6][7] Unlike traditional nanoparticle fillers, aerogel fillers enable better control of the distribution of the reinforcement in the matrix material, e.g., polymers. [8][9][10][11][12] Aerogels can be prepared by chemical vapor deposition, hydrothermal methods, freeze drying, and other approaches. [1,[13][14][15] These aerogels have demonstrated impressive reinforcement of polymer matrixes. [1,3] However, most aerogels are isotropic, which prevents their composites from being used in areas, such Aerogels are one of the most popular composite reinforcement materials because of their high porosity and their continuous and homogeneous network. Most aerogels are isotropic, thus leading to isotropic composites when they are used as fillers. This fundamentally limits their applications in areas where anisotropy is needed. Here, an anisotropic microhoneycomb cellulose nanofiber-(CellF)-carbon nanotube (CNT) aerogel (denoted MCCA) is reported that contains unidirectionally aligned penetrating microchannels, which is prepared by a unidirectional freeze-drying method, using the structure-directing function of the CellFs. Due to its anisotropic nature, MCCAreinforced polydimethylsilexane (denoted MCCA/PDMS) shows distinct anisotropic behavior, with the electrical conductivity and Young's modulus along the direction of penetrating microchannels being approximately twice those in the orthogonal direction. MCCA/PDMS is used to make "directional" strain sensors with electrical resistance as the output signal. They demonstrate a 92% sensitivity difference between the microchannel direction and its orthogonal direction. This approach can be used to prepare anisotropic MCCA-based composites with other polymers for different applications. SensorsThe ORCID identification number(s) for the author(s) of this article can be found under https://doi.

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Formation of Foam‐like Microstructural Carbon Material by Carbonization of Porous Coordination Polymers through a Ligand‐Assisted Foaming Process

Cited by 14 publications

References 49 publications

Bottom-up Formation of Carbon-Based Structures with Multilevel Hierarchy from MOF–Guest Polyhedra

Bottom-up Formation of Carbon-Based Structures with Multilevel Hierarchy from MOF–Guest Polyhedra

Controlling the morphology of metal–organic frameworks and porous carbon materials: metal oxides as primary architecture-directing agents

A Directional Strain Sensor Based on Anisotropic Microhoneycomb Cellulose Nanofiber‐Carbon Nanotube Hybrid Aerogels Prepared by Unidirectional Freeze Drying

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