Metalated Porous-Organic-Polymer Renders Mustard-Gas Simulant Harmless: Core Planarity Matters

TL;DR

This study develops metalated porous-organic-polymers (M-POPs) with open metal sites for effective catalytic oxidation of mustard-gas simulants, highlighting the importance of core planarity for performance.

Contribution

The paper introduces a new class of organic catalysts, M-POPs, with tailored core planarity that enhances catalytic activity for chemical decontamination.

Findings

Fe-Tt-POP achieved 99% oxidation of thioanisole in 13 hours.

Fe-Rb-POP showed 43% oxidation under the same conditions.

Core planarity significantly influences catalytic efficiency.

Abstract

The presence of open active metal sites in Metal-Organic Frameworks (MOFs) exhibit higher catalytic activity. However, rational accomplishment of MOFs in heterogeneous catalysis is limited due to coordination bonds. Recently balanced characteristic feature with combination of both the covalent bonds (structural stability) and open metal sites (single site catalysis) introduced an entirely organic alternative architecture named as Metalated Porous-Organic-Polymers (M-POPs). In this contribution, we demonstrate successful construction of two Fe-POPs (Fe-Tt-POP & Fe-Rb-POP) by ternary copolymerization approach for catalytic oxidative decontamination of different sulfur-based mustard gas simulants. Fe-Tt-POP exhibited superior catalytic performance for oxidation of the thioanisole (TA) studied in terms of conversion (99% after 13 h) in comparison with Fe-Rb-POP (43% after 13h). The remarkable difference in the mechanistic pathways towards catalytic performance for oxidation of TA was investigated by in situ operando Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) analysis, complemented by Density Functional Theory (DFT) computational study.