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

Abstract

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.

Near-infrared photothermal conversion of polyoxometalate-modified gold nanorods for plasmon-enhanced catalysis

“…As a simulation of the chemical warfare agent mustard gas, 43 the light oxidation of CEES to sulfoxide represents one of the effective methods for the detoxification of muon gas due to its nontoxicity, because the fully oxidized product is also highly toxic. 44 At present, most of the selective oxidations of CEES are carried out in the organic phase, [45][46][47] which are not very much suitable for applicable conditions. Therefore, developing catalysts with high activity in aqueous solution has become important.…”

Linker Independent Regioselective Protonation Triggered Detoxification of Sulfur Mustards with Smart Porous Organic Photopolymer

“…[9] The CWAs, also known as mustard gases (HDs) or toxic industrial chemicals, can cause severe and enduring injuries to the skin, eyes, and respiratory systems. [10] Due to the growing potential threats of a chemical assault using these gases, developing decontamination processes of HDs with higher efficiency becomes an important research subject for national security and public safety. [11] Various research groups have done landmark work in the last few years for the decontamination of HDs using catalytic materials, including metal-organic frameworks, [12] nanocrystalline metal oxides, [13] polyoxometalates, [14] and transition-metal carbides [15] respectively.…”

A critical review on emerging photoactive porous materials for sulfide oxidation and sulfur mustard decontamination

“…[1][2][3][4] CWAs have the capability of causing both immediate and longterm injury to the eyes, skin, and human respiratory system. 5 Disasters involving CWAs or toxic industrial chemicals are of particular concern due to their predisposition to inflict wide-Dr Priyanka Kalita received her BSc from B. Borooah College in 2015 and did her post-graduate degree at Gauhati University, Assam, in 2017. She received her doctoral degree from Gauhati University in 2022.…”

“…1–4 CWAs have the capability of causing both immediate and long-term injury to the eyes, skin, and human respiratory system. 5 Disasters involving CWAs or toxic industrial chemicals are of particular concern due to their predisposition to inflict widespread illness and fatality. 6 In 1993, considering the adverse effects, the use and stockpiling of CWAs were banned by United Nations members of the Chemical Weapons Convention (CWC).…”