Spray‐Coating of Catalytically Active MOF–Polythiourea through Postsynthetic Polymerization

Abstract

AUiO-66-NCS MOF was formed by postsynthetic modification of UiO-66-NH 2 .T he UiO-66-NCS MOFs displaysacirca 20-fold increase in activity against the chemical warfare agent simulant dimethyl-4-nitrophenyl phosphate (DMNP) compared to UiO-66-NH 2 ,making it the most active MOF materials using av alidated high-throughput screening. The À NCS functional groups provide reactive handles for postsynthetic polymerization of the MOFs into functional materials.T hese MOFs can be tethered to amine-terminated polypropylene polymers (Jeffamines) through af acile roomtemperature synthesis with no byproducts.The MOFs are then crosslinked into aMOF-polythiourea (MOF-PTU) composite material, maintaining the catalytic properties of the MOF and the flexibility of the polymer.This MOF-PTU hybrid material was spray-coated onto Nyco textile fibers,displaying excellent adhesion to the fiber surface.T he spray-coated fibers were screened for the degradation of DMNP and showed durable catalytic reactivity.

25 Jahre retikuläre Chemie

“…[196,206] Als Alternative wurde die Reaktion von Aminogruppen mit Isocyanatenund Isothiocyanaten entwickelt, die (Thio-)Harnstoff-Bindungen ohne Nebenprodukte erzeugen. [207] Zusätzlich wurde über Imin-Kondensationen an Amin-tragenden MOF-Liganden berichtet. Zum Beispiel ergab die Reaktion von IRMOF-3 mit Salicylaldehyd das Imin-Kondensationsprodukt über PSM (13 %U msatz).…”

“…Eine Einschränkung der berichteten Amin‐Amid‐PSM‐Reaktionen war die Bildung von sauren Nebenprodukten, die viele frühe MOFs abbauen konnten [196, 206] . Als Alternative wurde die Reaktion von Aminogruppen mit Isocyanaten und Isothiocyanaten entwickelt, die (Thio‐)Harnstoff‐Bindungen ohne Nebenprodukte erzeugen [207] . Zusätzlich wurde über Imin‐Kondensationen an Amin‐tragenden MOF‐Liganden berichtet.…”

Highly Breathable Chemically Protective MOF‐Fiber Catalysts

“…Therefore, research exploration is now turning to the synthetic approach and functional activity of flexible and robust MOF-fiber composite systems for practical implementation. [18,[30][31][32][33] A diverse set of MOF-polymer composites are being studied for adsorbent and catalytic functions using new synthetic approaches such as direct in situ solvothermal growth, [34] electrospinning, [35] solvent-free hot pressing, [36] direct assembly, [37] metal oxide coordination replication, [38] spray coating, [39] template-free aqueous synthesis, [40] and phase inversion process. [41] Previously, we successfully demonstrated that metal oxide thin films conformally deposited on the polymeric fiber surface via atomic layer deposition (ALD) help improve the uniformity of UiO-66-NH 2 MOF crystal growth with robust adhesion to the fiber surface.…”

“…Recently, many different Zr 6 -based MOF-fiber catalysts prepared by various creative approaches exhibited reasonably fast net hydrolysis rate (half-lives) of the nocuous chemicals. [33,39,40,44] However, except for only few cases, [45,46] catalytic performance on a per molarity of MOF basis (i.e., turnover frequency (TOF)) in MOF-fiber system is in general smaller than MOF powder counterparts. [37,39,47,48] In this respect, it is imperative to understand the critical parameters that further enhance the catalytic performance of the MOF films on the fiber systems, which could lead to an even faster net chemical detoxification rate.…”

25 Years of Reticular Chemistry

“…[196,206] As an alternative,t he reaction of amino groups with isocyanates and isothiocyanates was developed, which produce (thio)urea linkages without any byproducts. [207] Additionally,i mine condensations on amine-bearing MOF ligands were reported. For example,t he reaction of IRMOF-3 with salicylaldehyde produced the imine condensation product via PSM (13 % conversion).…”