Interface-engineered UiO-66 nanoparticles on porous carbon textiles for reactive protection against toxic 2-chloroethyl ethyl sulfide†

Abstract

Porous carbon textile composites with incorporated zirconium-based UiO-66 nanoparticles were synthesized using two approaches: a dip-and-dry post-synthesis deposition method and an in situ synthesis strategy in which UiO-66 nanoparticles were grown directly on the surface of carbon textiles. Pre-oxidation of the carbon textile significantly enhanced UiO-66 deposition and dispersion. The pre-oxidized composite textile synthesized through the in situ approach (CT-O-UiO-i) showed the highest UiO-66 loading of 6.7 wt%, which was more than four times higher than on the oxidized textile modified with pre-synthesized UiO-66 (CT-O-UiO-d). The surface area of CT-O-UiO-d and CT-O-UiO-i was 659 and 430 m² g⁻¹, respectively. The modified textiles effectively captured the mustard gas simulant, 2-chloroethyl ethyl sulfide (CEES), with weight uptakes reaching up to 396 mg g⁻¹ for CT-O-UiO-d. While the surface area was crucial for physical adsorption, UiO-66 enabled the chemical decomposition of CEES into less toxic compounds such as diethyl disulfide (DEDS) and ethyl vinyl sulfide (EVS). CT-O-UiO-i exhibited the highest reactivity, primarily converting CEES to EVS via dehydrohalogenation. This was attributed to the high dispersion and strong anchoring of UiO-66, increasing the number and accessibility of Lewis acidic sites. Therefore, this study highlights the potential of MOF-modified carbon textiles as functional materials that combine physical and reactive adsorption to ensure effective protection against this chemical warfare agent.