Assessing Detoxification Performance of Metal Hydroxide@Polymer Composites Prepared via Matrix-Incorporation and Spray-Coating Techniques

Abstract

Polymer-based composites with tunable physiochemical properties are great candidates for efficient destruction of toxic chemicals and vapors. Herein, we report the development of metal hydoxide@polymer composites via matrix-incorporation and spray-coating methods and the assessment of the impact of different preparation methods on their physiochemical properties and detoxification performance. Specifically, Zr(OH) 4 and Ce(OH) 4 were used to enhance the catalytic activity of Ultem, Matrimid, and PIM-1 polymers toward hydrolysis of dimethyl 4-nitrophenylphosphonate (DMNP) simulant. Two different preparation techniques were employed to assess the structure-performance relations in the developed composites in terms of DMNP detoxification performance. The results obtained indicated that surface-coated metal hydoxide@polymer composites outperformed their respective incorporated analogues for both Zr(OH) 4 and Ce(OH) 4 due to the presence of more accessible surface active sites. Moreover, it was found that Ce(OH) 4 gave rise to a faster detoxification rate than Zr(OH) 4 in both matrix-incorporated and surfacecoated composites owing to higher Lewis acidity of Ce(OH) 4 than Zr(OH) 4 . Among the materials investigated, the best-performing material was found to be surface-coated Ce(OH) 4 @PIM-1, which exhibited the fastest DMNP detoxification rate of 0.08 min −1 and the shortest half-life of 8.67 min. The findings of this investigation highlight the potential of the spray-coating method for fabricating composites effective for detoxification of toxic chemicals and vapors.

Gas-Phase Adsorption of Dimethyl Methylphosphonate over Ce(OH)4@PIM-1 Composites Prepared via Matrix Incorporation and Surface Coating Methods

“…PIMs are highly cross-linked polymers with a unique combination of high surface area, permanent porosity, and tunable functionalities, which make them attractive for adsorption processes. Among various PIMs, PIM-1, as the most studied flagship PIM, has garnered significant interest due to its exceptional microporosity and potential for selective gas-phase adsorption of specific molecules like DMMP. , Moreover, PIM-1’s excellent thermal stability enhances its effectiveness in demanding environments. , As reported by Parsons group, its notable selectivity toward DMMP makes it an appealing choice for investigating CWA adsorption, detoxification, and destruction processes. In particular, PIM-1’s versatile nature finds use in catalytic filters, effectively removing hazardous compounds such as DMMP from air streams …”

“…In our previous works, , we showed that incorporatioon of metal hydroxides such as cerium hydroxide (Ce­(OH) 4 ) or zirconium hydroxide (Zr­(OH) 4 ) into glassy polymers can enhance stability and reactivity of the host polymers when exposed to hazardous substances due to their remarkable physicochemical properties. , In particular, Ce­(OH) 4 is an effective material for adsorption due to its Lewis acidic properties . Lewis acids can accept electron pairs from Lewis bases.…”

Liquid-Phase Adsorption of Dimethyl Methylphosphonate on Poly(ether imide) and its Metal Hydroxide-Integrated Composites

“…In recent years, polymers have gained significant attention as potential adsorbents for DMMP and other simulants due to their adaptable structures, versatile functionalization possibilities, and ease of processability. Notably, organic compounds with hydrogen bond donors have shown efficacy in selectively adsorbing DMMP through hydrogen bond interactions. − Among these materials, poly­(ether imide) (PEI) or Ultem can potentially be a promising candidate for DMMP or CWA adsorption and detoxification . Ultem’s inherent shape-memory properties allow it to return to a predefined shape after deformation, a significant attribute for adaptive filtration systems. , This combined with its self-healing capabilities extends its longevity and performance under challenging conditions.…”

“…Furthermore, its remarkable mechanical strength ensures the stability and integrity of the adsorbent, even under the stress of high adsorbate loadings. − Moreover, the presence of diverse functional groups in Ultem may allow for potential interactions with DMMP, thus enhancing the adsorption efficacy. Economically, Ultem stands out for being cost-effective and straightforward to prepare. , Crucially, Ultem facilitates nondestructive adsorption of DMMP, preserving the molecular integrity of the adsorbate, which is pivotal for subsequent analytical or decontamination processes. Overall, these attributes solidify Ultem’s position as a frontrunner in the scope of polymer-based adsorbents for DMMP and CWAs adsorption.…”

“…Ce­(OH) 4 and Zr­(OH) 4 demonstrate exceptional efficacy in liquid-phase DMMP adsorption, primarily attributed to their unique surface chemistries. ,, Their inherent Lewis acidity allows for effective interactions with the Lewis base components present in DMMP, particularly its phosphonate groups. This interplay between the Lewis acidic sites of the metal hydroxides and the Lewis basic nature of DMMP ensures robust and selective adsorption in liquid-phase environments. ,, Polymer/metal hydroxide composites, such as those integrating Ultem with Ce­(OH) 4 or Zr­(OH) 4 , present marked advantages for DMMP adsorption.…”