Direct Fabrication of Free‐Standing MOF Superstructures with Desired Shapes by Micro‐Confined Interfacial Synthesis

Abstract

Recently, metal-organic frameworks (MOFs) with multifunctional pore chemistry have been intensively investigated for positioning the desired morphology at specific locations onto substrates for manufacturing devices. Herein, we develop a micro-confined interfacial synthesis (MIS) approach for fabrication of a variety of free-standing MOF superstructures with desired shapes. This approach for engineering MOFs provides three key features: 1) in situ synthesis of various free-standing MOF superstructures with controlled compositions, shape, and thickness using a mold membrane; 2) adding magnetic functionality into MOF superstructures by loading with Fe3 O4 nanoparticles; 3) transferring the synthesized MOF superstructural array on to flat or curved surface of various substrates. The MIS route with versatile potential opens the door for a number of new perspectives in various applications.

Solvent mediated morphology control of zinc MOFs as carbon templates for application in supercapacitors

“…[6][7][8][9][10] To meet the ever-growing demand of MOFs in a myriad of potential applications, considerable research efforts have been devoted to controlling the size and morphology of MOFs in a nanosize regime, which can tailor the physical/chemical properties without changing the chemical compositions. 11,12 Structuring MOFs at the nano-and mesoscopic scale has been accomplished by various methodologies [11][12][13] such as microwave assisted synthesis, 14 mechanochemical synthesis, 15 interfacial assembly, 16,17 emulsion templating, 18 and coordination modulation. 19,20 However, these approaches usually require specic reactors and equipment, or additional additives and modulators that are sometimes restricted to work in a narrow synthesis parameter window only.…”

Grenzflächenpolymerisation: Von der Chemie zu funktionellen Materialien

“…Durch die Beschränkung der Grenzfläche auf einen Mikrobereich mit bestimmten Formen (diskrete wässrige Phase oder Grenzfläche) wurden freistehende MOF‐Mikroschichten mit definierter Größe und Geometrie hergestellt, die auch auf die Oberfläche verschiedener Substrate übertragen werden können (Abbildung 9 b). [109b, 110] Darüber hinaus wurde die Grenzflächenpolykoordination auch zur Bildung einer einheitlichen selektiven MOF‐Schicht auf porösen Substraten genutzt [46, 111] . Brown et al.…”

Large‐Area, Freestanding MOF Films of Planar, Curvilinear, or Micropatterned Topographies

“…,. Most recently, Ameloot and co‐workers demonstrated deposition and patterning of approximately 100‐nm‐thick MOF films by chemical vapor deposition (CVD) method whereas Kim's group demonstrated film growth at and subsequent transfer from liquid–liquid interfaces . Still, the largest freestanding (as opposed to surface‐supported) MOF films made to date are only up to around a centimeter across ,.…”

“…Most recently, Ameloot and co‐workers demonstrated deposition and patterning of approximately 100‐nm‐thick MOF films by chemical vapor deposition (CVD) method whereas Kim's group demonstrated film growth at and subsequent transfer from liquid–liquid interfaces . Still, the largest freestanding (as opposed to surface‐supported) MOF films made to date are only up to around a centimeter across ,. Our motivation herein is to develop a method that would form large‐scale MOF materials on a benchtop, be robust with respect to experimental parameters, and not require any specialized equipment.…”