Water sensitivity of heteroepitaxial Cu-MOF films: dissolution and re-crystallization of 3D-oriented MOF superstructures

Brandner, Lea A.; Linares-Moreau, Mercedes; Zhou, Guojun; Amenitsch, Heinz; Dal Zilio, Simone; Huang, Zhehao; Doonan, Christian; Falcaro, Paolo

doi:10.1039/d3sc04135b

Cited by 4 publications

(5 citation statements)

References 71 publications

(126 reference statements)

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“…32 Additional studies on the stability of Cu-MOFs support the need for enhanced stability in these complexes. 33–35…”

Section: Resultsmentioning

confidence: 99%

A water-stable copper-based nanosized metal–organic framework for discriminative sensing of amines

Álvarez García,

Álvarez Rubiera,

Gutiérrez Armayor

et al. 2024

Mater. Adv.

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“…32 Additional studies on the stability of Cu-MOFs support the need for enhanced stability in these complexes. 33–35…”

Section: Resultsmentioning

confidence: 99%

A water-stable copper-based nanosized metal–organic framework for discriminative sensing of amines

Álvarez García,

Álvarez Rubiera,

Gutiérrez Armayor

et al. 2024

Mater. Adv.

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“…Additionally, we believe advancements in microscopy, such as TEM, will benefit this field providing accurate textural maps showcasing both local crystal domain and pore orientation. For example, in the case of heteroepitaxial growth, electron diffraction performed with transmission electron microscopy (TEM) has been used to assess local heteroepitaxial relationships at the interface of ceramics‐to‐MOF [ 44 ] or MOF‐to‐MOF [ 268 ] heterostructures. We note that TEM‐based techniques such as orientation and phase mapping [ 89,90 ] have been successfully applied to metals, oxides and semiconductors to analyze nanoscale crystal orientation and construct orientational maps in areas of tens of microns.…”

Section: Discussionmentioning

confidence: 99%

Section: New Methodsmentioning

confidence: 99%

“…demonstrated a similar concept for the MOF‐to‐MOF transformation from 3D‐oriented films of Cu 2 (BDC) 2 DABCO to 3D‐oriented Cu 2 (BDC) 2 (Figure 13e). [ 268 ] The Cu 2 (BDC) 2 DABCO films were prepared via the heteroepitaxial growth from sacrificial Cu(OH) 2 nanostructures and exposed to different water loadings. Specifically, when films were exposed to 80% relative humidity (RH) and liquid water, SEM images displayed a change in morphology from cuboid crystals (Cu 2 (BDC) 2 DABCO) to smaller plate‐like crystals of Cu 2 (BDC) 2 (Figure 13f).…”

Section: New Methodsmentioning

confidence: 99%

“…The MOF‐to‐MOF transformation was attributed to a dissolution‐recrystallization mechanism due to the high lattice matching of the two frameworks showing that the heteroepitaxial recrystallization mechanism can occur in both, single‐crystal [ 267 ] and polycrystalline systems. [ 268 ]…”

Section: New Methodsmentioning

confidence: 99%

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Fabrication of Oriented Polycrystalline MOF Superstructures

Linares‐Moreau,

Brandner,

Velásquez‐Hernández

et al. 2023

Advanced Materials

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The field of metal‐organic frameworks (MOFs) has progressed beyond the design and exploration of powdery and single‐crystalline materials. A current challenge is the fabrication of organized superstructures that can harness the directional properties of the individual constituent MOF crystals. To date, the progress in the fabrication methods of polycrystalline MOF superstructures has led to close‐packed structures with defined crystalline orientation. By controlling the crystalline orientation, the MOF pore channels of the constituent crystals can be aligned along specific directions: these systems possess anisotropic properties including enhanced diffusion along specific directions, preferential orientation of guest species, and protection of functional guests. In this perspective, we discuss the current status of MOF research in the fabrication of oriented polycrystalline superstructures focusing on the specific crystalline directions of orientation. Three methods are examined in detail: the assembly from colloidal MOF solutions, the use of external fields for the alignment of MOF particles, and the heteroepitaxial ceramic‐to‐MOF growth. This perspective aims at promoting the progress of this field of research and inspiring the development of new protocols for the preparation of MOF systems with oriented pore channels, to enable advanced MOF‐based devices with anisotropic properties.

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Ordered Transfer from 3D‐Oriented MOF Superstructures to Polymeric Films: Microfabrication, Enhanced Chemical Stability, and Anisotropic Fluorescent Patterns

Brandner,

Marmiroli,

Linares‐Moreau

et al. 2024

Advanced Materials

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Films and patterns of 3D‐oriented metal‐organic frameworks (MOFs) afford well‐ordered pore structures extending across centimeter‐scale areas. These macroscopic domains of aligned pores are pivotal to enhance diffusion along specific pathways and orient functional guests. The anisotropic properties emerging from this alignment are beneficial for applications in ion conductivity and photonics. However, the structure of 3D‐oriented MOF films and patterns can rapidly degrade under humid and acidic conditions. Thus, more durable 3D‐ordered porous systems are desired for practical applications. Here, oriented porous polymer films and patterns are prepared by using heteroepitaxially oriented N3‐functionalized MOF films as precursor materials. The film fabrication protocol utilizes an azide–alkyne cycloaddition on the Cu2(AzBPDC)2DABCO MOF. The micropatterning protocol exploits the X‐ray sensitivity of azide groups in Cu2(AzBPDC)2DABCO, enabling selective degradation in the irradiated areas. The masked regions of the MOF film retain their N3‐functionality, allowing for subsequent cross‐linking through azide‐alkyne coupling. Subsequent acidic treatment removes the Cu ions from the MOF, yielding porous polymer micro‐patterns. The polymer has high chemical stability and shows an anisotropic fluorescent response. The use of 3D‐oriented MOF systems as precursors for the fabrication of oriented porous polymers will facilitate the progress of optical components for photonic applications.

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Water sensitivity of heteroepitaxial Cu-MOF films: dissolution and re-crystallization of 3D-oriented MOF superstructures

Abstract: 3D-oriented metal-organic framework (MOF) films and patterns have recently emerged as promising platforms for sensing and photonic applications. These oriented polycrystalline materials are typically prepared by heteroepitaxial growth from aligned...

Cited by 4 publications

References 71 publications

A water-stable copper-based nanosized metal–organic framework for discriminative sensing of amines

A water-stable copper-based nanosized metal–organic framework for discriminative sensing of amines

Fabrication of Oriented Polycrystalline MOF Superstructures

Ordered Transfer from 3D‐Oriented MOF Superstructures to Polymeric Films: Microfabrication, Enhanced Chemical Stability, and Anisotropic Fluorescent Patterns

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