Shaping of Flexible Metal‐Organic Frameworks: Combining Macroscopic Stability and Framework Flexibility

Kriesten, Martin; Schmitz, Jürgen Vargas; Siegel, Jonas; Smith, Christopher; Kaspereit, Malte; Hartmann, Martin

doi:10.1002/ejic.201901100

Cited by 48 publications

(50 citation statements)

References 91 publications

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“…A particle may comprise several smaller individual nanocrystals. Such matrix-induced stiffening has been already reported for MIL-53 [84] in glasses and composites [85]. However, more systematic work is needed to achieve a better understanding and quantification of such effects.…”

Section: Trends In Chemistrymentioning

confidence: 70%

From Macro- to Nanoscale: Finite Size Effects on Metal–Organic Framework Switchability

Ehrling

Miura

Senkovska

et al. 2021

Trends in Chemistry

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Switchable metal-organic frameworks (MOFs) standt out for potential applications in energy storage, separation, sensing, and catalysis. The understanding of MOF switchability mechanisms has progressed significantly over the past two decades. Nanostructuring is essential for the integration of such materials into thin films, hierarchical composites, and membranes and for biological applications. However, downsizing below critical dimensions causes dramatic changes in the dynamic behavior and responsiveness towards external stimuli. We discuss the most important experimental findings and derive general guidelines and hypotheses of relevance for the impact of crystal size on switchability. Understanding nanostructure thermodynamics and implications for the tailoring of dynamic porous systems requires an interdisciplinary approach, advanced physical characterization techniques, and new modeling strategies to cover a wider range of time and length scales. MOF Switchability and FunctionalityMOFs are among the most porous systems, with great potential in diverse applications such as energy storage, separation, air purification, and many more [1,2]. An outstanding feature, compared with other, traditional porous materials, is their ability to transform (switch) between different phases with well-defined crystalline structures triggered by external stimuli, often by guest inclusion [3,4]. The latter leads, in some cases, to important improvements in gas separation or storage due to ultrahigh selectivity [5] or high deliverable capacity [6]. The terms 'flexible MOF', 'soft porous crystals', and 'switchable MOF' are used synonymously [7,8]. An important aspect indicated by the term 'switchability' is the stepwise (first order) character of the structural transition between two phases (bistability). Recently, even multistable systems have emerged, leading to remarkable recognition effects [9,10]. These phase transitions induced by external stimuli (e.g., changes in temperature, external pressure, gas pressure, vapor pressure, or electromagnetic radiation) are associated with a latent heat of transformation, L, governing the energetics of the bulk phase transition. An activation barrier (E A or ΔG ǂ ) governs the kinetics and potential windows for metastable states. Nucleation (for nucleation theory see Glossary and see supplemental information online for additional Glossary terms) of the new solid phase is an important characteristic of the solid-solid phase transition. Nevertheless, the fluid kinetics of adsorption and, potentially, fluid nucleation kinetics may also play a role. HighlightsSwitchable metal-organic frameworks (MOFs) conquer advanced applications in energy storage, sensing, gas separation, catalysis, and biomedicine. They benefit from unique adsorption characteristics and responsive behavior leading to anomalously high separation selectivity and deliverable storage capacity.Nanostructuring provides an effective means to tailor the responsive behavior of switchable MOFs. The characteristic switching pressure d...

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Section: Trends In Chemistrymentioning

confidence: 70%

From Macro- to Nanoscale: Finite Size Effects on Metal–Organic Framework Switchability

Ehrling

Miura

Senkovska

et al. 2021

Trends in Chemistry

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“…The structural transitions of SPCs previously introduced cause major volume changes, posing challenges for integrating such solids in adsorption‐based systems . Although the incorporation of SPCs in adaptive matrices may compensate for such volume changes, achieving dynamic properties without having major changes in the solid volume is increasingly gaining attention. Pyrazine, para ‐substituted phenylenes, and substituted naphthalenes incorporated in PCPs exhibit significant thermally induced rotation, which can dynamically alter the pore accessibility, thus changing the apparent adsorption volume .…”

Section: Structural Softness Transitions and Dynamicsmentioning

confidence: 99%

Chemistry of Soft Porous Crystals: Structural Dynamics and Gas Adsorption Properties

2020

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In this Minireview, we discuss the fundamental chemistry of soft porous crystals (SPCs) by characterizing their common structural features and the resulting structural softness and transitions. In particular, we focus on the recently emerging properties based on metastable transitions and those arising from local dynamics. By comparing the resulting adsorption properties to those of commonly applied rigid adsorbents, we highlight the potential of SPCs to revolutionize adsorption‐based technologies, considering our current understanding of the thermodynamic and kinetic aspects. We provide brief outlines for the experimental and computational characterization of such phenomena and offer an outlook toward next‐generation SPCs likely to be discovered in the next decade.

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“…Extrusion of Al-based MIL-53 MOF was studied by Kriesten et al [87]. They investigated more specifically the framework "breathing" properties of MIL-53 and its evolution upon shaping.…”

Section: Materials Advances Accepted Manuscriptmentioning

confidence: 99%

From metal–organic framework powders to shaped solids: recent developments and challenges

et al. 2021

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Shaping of Flexible Metal‐Organic Frameworks: Combining Macroscopic Stability and Framework Flexibility

Cited by 48 publications

References 91 publications

From Macro- to Nanoscale: Finite Size Effects on Metal–Organic Framework Switchability

From Macro- to Nanoscale: Finite Size Effects on Metal–Organic Framework Switchability

Chemistry of Soft Porous Crystals: Structural Dynamics and Gas Adsorption Properties

From metal–organic framework powders to shaped solids: recent developments and challenges

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