Toxic Organophosphate Hydrolysis Using Nanofiber-Templated UiO-66-NH2 Metal-Organic Framework Polycrystalline Cylinders

Derek B Dwyer; Dennis T Lee; Steven Boyer; William E Bernier; Gregory N Parsons; Wayne E Jones Jr

doi:10.1021/acsami.8b08167

Toxic Organophosphate Hydrolysis Using Nanofiber-Templated UiO-66-NH₂ Metal-Organic Framework Polycrystalline Cylinders

ACS Appl Mater Interfaces. 2018 Aug 1;10(30):25794-25803. doi: 10.1021/acsami.8b08167. Epub 2018 Jul 19.

Authors

Derek B Dwyer¹, Dennis T Lee², Steven Boyer¹, William E Bernier¹, Gregory N Parsons², Wayne E Jones Jr^{1

3}

Affiliations

¹ Binghamton University State University of New York , 4400 Vestal Parkway East , Binghamton , New York 13902 , United States.
² Department of Chemical and Biomolecular Engineering , North Carolina State University , 911 Partners Way , Raleigh , North Carolina 27695 , United States.
³ University of New Hampshire , 105 Main Street , Durham , New Hampshire 03824 , United States.

PMID: 29972296
DOI: 10.1021/acsami.8b08167

Abstract

Metal organic frameworks (MOFs), the UiO series in particular, have attracted much attention because of the high surface area and ability to capture and decontaminate chemical warfare agents. Much work has been done on incorporating these MOFs into or onto textile materials while retaining the desirable properties of the MOF. Many different techniques have been explored to achieve this. Atomic layer deposition (ALD) of TiO₂ followed by solvothermal synthesis of MOF has become one of the most adaptable techniques for growing MOFs on the surface of many different polymer fabric materials. However, little work has been done with using this technique on polymer composite materials. In this work, UiO-66-NH₂ was grown onto the surface of poly(methyl methacrylate) (PMMA)/Ti(OH)₄ and poly(vinylidene fluoride) (PVDF)/Ti(OH)₄ composite fibers by first modifying the surface with ALD of TiO₂ (@TiO₂) followed by solvothermal synthesis of MOF (@MOF). The catalytic activity of these materials was then evaluated using the simulant paraoxon-methyl (DMNP). These new MOF-functionalized composite fabrics were compared to polyamide-6 (PA-6)@TiO₂@MOF- and polypropylene (PP)@TiO₂@MOF-functionalized fabrics. PMMA/Ti(OH)₄@TiO₂@MOF fibers resulted in unique hollowed fibers with high surface area of 264 m²/g and fast catalytic activity. The catalytic activity of these samples was found to be related to the active MOF mass fraction on the MOF-functionalized composite fabric, with the hollowed PMMA/Ti(OH)₄@TiO₂@MOF having the highest weight percent of active MOF and a DMNP t_1/2 of 26 min followed by PA-6@TiO₂@MOF with 45 min, PVDF/Ti(OH)₄@TiO₂@MOF with 61 min, and PP@TiO₂@MOF with 83 min.

Keywords: atomic layer deposition; hollow fiber structures MOF/fiber polymer composite; metal−organic frameworks; nanofibers; toxic organophosphates.