Porphyrin-Moiety-Functionalized Metal–Organic Layers Exhibiting Catalytic Capabilities for Detoxifying Nerve Agent and Blister Agent Simulants

Abstract

The development of very efficient bifunctional catalysts for the simultaneous detoxification of two kinds of the deadliest chemical warfare agents (CWAs), nerve agent and blister agent, is highly desirable. In this study, two porphyrin-based ligands [tetrakis(4-carboxyphenyl) porphyrin (TCPP) and protoporphyrin IX (PPIX)] are introduced into 2D Zr-1,3,5-tris(4-carboxyphenyl)benzene (BTB) metal−organic layers (MOLs), composed of six-connected Zr 6 nodes and the tritopic carboxylate ligand BTB, by a solvent-assisted ligand incorporation method. The loads of TCPP and PPIX are 6.4 and 10.9 wt %, respectively. The detoxification of simulants of the nerve agent and the blister agent was conducted to investigate the catalytic activity of porphyrin-moiety-functionalized MOLs. The reaction half-life of optimal TCPP-functionalized MOL catalyzing the hydrolysis of a nerve agent simulant is only 2.8 min, meanwhile, the half-life of the selective catalytic oxidation of a blister agent simulant is only 1.2 min under LED illumination. More importantly, such a degradation half-life is only about 4 min under natural sunlight (∼60 mW/cm 2 ). To our knowledge, TCPP-functionalized MOL is by far the most efficient catalyst for blister agent simulant degradation under solar light. Therefore, 2D ultrathin MOLs on demand appear to be a promising and efficient material platform for the development of bifunctional catalysts for CWA protection.

Modulated Self-Assembly of Catalytically Active Metal–Organic Nanosheets Containing Zr6 Clusters and Dicarboxylate Ligands

“…60 The GUF-14 hns MONs were able to completely hydrolyze DMNP within 12 min (Figure 5b,c), with a t 1/2 of ∼6.5 min, outperforming several other known Zr 6 cluster-based MOFs such as PCN-222, NU-1000 and UiO-66, 59 again indicative of the high accessibility of the coordinatively unsaturated Zr 6 cluster. However, the t 1/2 of the GUF-14 hns phase is higher than those reported for the Zr-BTB MON (t 1/2 = 2.1 min) 61,62 and the benchmark catalyst MOF-808(Zr) (t 1/2 = <0.5 min), 58 suggesting that further optimization of structure or activation would be required to closely compete with sector-leading materials.…”

Mechanically Enhanced Detoxification of Chemical Warfare Agent Simulants by a Two-Dimensional Piezoresponsive Metal–Organic Framework

“…As reported, DMNP can undergo hydrolysis to form p-Nitrophenol. Consequently, the detoxification performance of the prepared MOF can be evaluated by monitoring the concentration change in p-Nitrophenol [1]. The results indicate that, in a sonic environment, the conversion remains relatively unchanged after 100 min, indicating that the DMNP lacks self-degradation capabilities under stirring or ultrasonic conditions (Figure 6e).…”

“…During the assembly process of UiO-66-F 4 , the absence or unsaturated coordination of Zr-O clusters can lead to a significant number of metal node or ligand defects, ultimately endowing UiO-66-F 4 with remarkable catalytic capabilities, even without any external assistance. When the UiO-66-F 4 nanosheets are employed for the removal of CWA simulants, the unsaturated coordination sites can directly react with the ester group of DMNP, thereby achieving the aim of detoxification [1]. After the application of mechanical vibration, the band gap of the nanocrystals widens significantly, leading to the polarization effect.…”

“…Chemical warfare agents (CWAs) refer to various chemical substances with severe toxicity used for war purposes, capable of poisoning or killing enemy humans, animals, and plants on a large scale. In recent years, CWAs have been one of the crucial means for terrorists and extremist organizations to enforce terrorist activities and war activities due to their large killing ability, wide working range, strong concealment, and low cost [1][2][3]. Consequently, due to their terrible toxicity, the quick detoxification of CWAs has become one of the critical demands in preventing CWA attacks [4,5].…”

Zr-MOF Nanosheets Vertically Grown on Fabrics for Rapid Catalytic Elimination of Nerve Agent Simulants

“…After 100 min, PP/MOFNS-3 fabric adsorbed about 23.0% p-nitrophenol, and MOF itself adsorbed about 20.7%, which indicates that the main reason for PP/MOFNS-3 fabric adsorption is MOF absorption (Figure S20). In order to further confirm that DMNP can be completely degraded by PP/MOFNS Fabrics, the degradation products after reaction for 120 min were characterized by 31 P NMR. As shown in Figure 7d, the peak at −4.15 ppm, which corresponds to DMNP, disappears at the end of the reaction, while the peak at 3.01 ppm corresponding to the degradation product, DMP appears.…”