Functionalized MOF-Coated Ce(OH)4@PIM-1 Composites for Enhanced Detoxification of Dimethyl 4-Nitrophenyl Phosphate

Abstract

Metal–organic framework (MOF)-coated polymer composites have emerged as highly promising materials for catalytic applications, particularly in the degradation of chemical warfare agents (CWAs) and their simulants. In this study, we present the design and development of MOF-coated Ce(OH)4-incorporated PIM-1 composites via supramolecular assembly. Three different MOFs, namely, UiO-66, UiO-67, and MOF-808, and their bromine (Br)- and amine (−NH2)-functionalized derivatives were studied. The catalytic performance of the composites was evaluated through hydrolysis of dimethyl 4-nitrophenyl phosphate (DMNP), as a nerve agent simulant. Among the bare MOFs, MOF-808-NH2exhibited the highest reactivity, with a degradation half-life (τ1/2) and a rate constant (k) of 2.13 and 0.33 min–1, respectively. Upon deposition of MOF-808-NH2onto Ce(OH)4-incorporated PIM-1-COOH (Ce(OH)4@PIM-1-COOH), the τ1/2and k values shifted to 4.58 and 0.15 min–1, respectively. This composite demonstrated superior catalytic performance, achieving complete DMNP degradation within 15 min due to the synergistic effects of Brønsted acidity from PIM-1-COOH and Lewis acidity from Ce(OH)4and MOF-808-NH2. These findings underscore the potential of MOF-coated polymer composites in catalytic detoxification applications.