4.8 Article

A Catalytically Accessible Polyoxometalate in a Porous Fiber for Degradation of a Mustard Gas Simulant

Journal

ACS APPLIED MATERIALS & INTERFACES
Volume 14, Issue 14, Pages 16687-16693

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acsami.2c01584

Keywords

porous polymers; polymers of intrinsic microporosity (PIMs); polyoxometalates (POMs); composite fibers; chemical warfare agents

Funding

  1. Defense Threat Reduction Agency [HDTRA1-19-10010]
  2. Army Research Office [W911NF-181-0359]
  3. NSF [CHE-1048773, NSF ECCS-2025633, ECCS-2025633]
  4. Northwestern's MRSEC program (NSF) [DMR-1720139]
  5. National Science Foundation Graduate Research Fellowship [DGE-1842165]

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Polyoxometalates (POMs) are versatile materials for chemical catalysis due to their tunable acidity and rich redox properties. In this study, a pure inorganic Keggin-type POM was anchored to a polymer support to fabricate composite materials. The composite fibers maintained the catalytic activity of the POM and showed potential for use in protective equipment.
Polyoxometalates (POMs) are versatile materials for chemical catalysis due to their tunable acidity and rich redox properties. While POMs have attracted significant attention in homogeneous catalysis, challenges regarding aggregation and instability in solvents often prevent the wide implementation of POMs as heterogeneous catalysts. Therefore, the successful incorporation of a POM into a solid support, such as a polymer, is desirable for practical applications where unique functionalities of the POM combine with the advantages of the polymer. In this work, we showcase how polymers of intrinsic microporosity (PIMs) can serve as matrices for anchoring a pure inorganic Keggin-type POM (H3PW12O40) to fabricate PIM-based composite materials. Specifically, we found that PIMs installed with amidoxime functionalities could successfully attach POMs (PW12@PIM-1-AO) without self-segregation. Furthermore, we fabricated porous fibrous mats via electrospinning of the PIM-POM composites. Comprehensive characterization confirmed the integrity of the POM in the composite material. Following this, we demonstrated that the incorporated POMs in the composite fibers maintained their innate catalytic activity for the oxidative degradation of 2-chloroethyl ethyl sulfide, a sulfur mustard simulant, in the presence of hydrogen peroxide as the oxidant. Ultimately, our work highlights that PIM-based hybrid materials provide a potential route for implementing these reactive fiber mats into protective equipment.

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