4.8 Article

Metal Oxide Catalysts for the Synthesis of Covalent Organic Frameworks and One-Step Preparation of Covalent Organic Framework-Based Composites

Journal

CHEMISTRY OF MATERIALS
Volume 33, Issue 15, Pages 6158-6165

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.chemmater.1c01747

Keywords

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Funding

  1. Army Research Laboratory [W911NF-18-2-0062]
  2. Welch Foundation for Chemical Research [C-1888]
  3. NSF Nanosystems Engineering Research Center for Nanotechnology-Enabled Water Treatment [ERC-1449500]

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The study introduces a one-pot synthesis method for COFs using a variety of metal oxides as catalysts to synthesize highly crystalline and porous COFs. It confirms that these metal oxides can effectively catalyze the synthesis of imine COFs.
The integration of covalent organic frameworks (COFs) with inorganic materials provides opportunities to develop a new class of composite materials with high surface areas and novel functionalities relevant to photocatalysis, chemical adsorption, and magnetic resonance imaging. However, current methods for the preparation of COF-based composites require challenging, multistep synthetic protocols. Herein, we report a one-pot synthesis approach using a wide range of metal oxides to catalyze the synthesis of highly crystalline and porous COFs. We found that a large variety of metal oxides served as effective catalysts for the synthesis of imine COFs, including niobium(V) oxide (Nb2O5), nickel(II) oxide (NiO), manganese(IV) dioxide (MnO2), ruthenium(IV) oxide (RuO2), zinc(II) oxide (ZnO), lead(II) oxide (PbO), tellurium(IV) dioxide (TeO2 ), tin(IV) oxide (SnO2), manganese(III) oxide (Mn2O3 ), zirconium(IV) dioxide (ZrO2 and aluminum(III) oxide (Al2O3). Nb2O5 was effective for the synthesis of a wide range of COFs with different functional groups and pore sizes, and these reactions produced a metal oxide/COF composite. By using Fe3O4 nanoparticles (NPs) as the catalyst, we produced COF-based nanocomposites with Fe3O4 NPs distributed throughout the final COF product. The Fe3O4/COF nanocomposite had a high surface area of 2196 m(2) g(-1). This work demonstrates a class of novel, low-cost catalysts for synthesizing COFs and a new approach to produce metal oxide/COF composite materials.

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