Graphene Oxide and Metal-Organic Framework-Based Breathable Barrier Membranes for Toxic Vapors

Abstract

Garments protective against chemical warfare agents (CWAs) or accidently released toxic chemicals must block the transport of toxic gases/vapors for a substantial time and allow moisture transport for breathability. These demands are challenging: either the barriers block CWAs effectively but have poor breathability or barriers have excellent breathability but cannot block CWAs well. Existing protective garments employ large amounts of active carbon, making them quite heavy. Metal-organic framework (MOF)-based adsorbents are being investigated as sorbents for CWAs. Breathable laminate of graphene oxide (GO) flakes supported on a porous membrane reduces permeation rates of CWA simulants substantially. We developed a multilayered membrane-based flexible barrier: GO laminate-based membrane over a MOF nanocrystal-filled expanded polytetrafluorethylene (ePTFE) membrane having submicrometer pores. The GO laminate-based layer developed a steady breakthrough concentration level almost 2 orders of magnitude below the usual breakthrough level. This highly reduced level of CWA was blocked by the MOF nanocrystal-filled membrane substrate layer over a highly extended period. We demonstrated the blocking of CWAs, mustard (HD), soman (GD), a sarin simulant [dimethyl methyl phosphonate (DMMP)], and ammonia for an extended period while the moisture transmission rate was substantial. The times for complete blockage of ammonia, HD, GD, and DMMP were 2750 min, 1075 min, 176 min, and 7 days, respectively. This remarkable performance resulted from a very low steady-state penetrant permeation through GO-laminate membrane and substantial penetrant sorption by MOF nanocrystals; furthermore, both layers show high moisture vapor transmission.

Keywords: breathable fabric; chemical warfare agents; graphene oxide laminate membrane; metal−organic framework; multilayer barrier structure; nano-scale packed bed.