In recent years, significant attention has been directed toward evaluating the reactivity of diverse polymers to gauge their catalytic activity against hazardous chemicals. Among these polymers, PIM-1 has emerged as an exceptional candidate due to its noteworthy attributes including high surface area, excellent solubility, and the capability to fine-tune the nitrile functional groups along its polymeric backbone. In this study, we explored the impact of different functional groups, such as amidoxime (AX), aldoxime (OX), and carboxylate (COOH), on the degradation of dimethyl 4-nitrophenylphosphonate (DMNP) in comparison to pure PIM-1 and their respective Ce(OH)₄-loaded polymer composites. Remarkably, the PIM-1-AX analog exhibited the highest degree of catalytic activity (ca. 100%) among the functional groups investigated under 24 h, due to its high nucleophilicity, whereas under 1 h, Ce(OH)₄@PIM-1-COOH outperformed other materials by displaying an initial hydrolysis rate of 0.058 μmol/s and a half-time of 0.38 min, on the account of its high Lewis acidity, stemming from the Ce⁴⁺ coupled with the Bronsted carboxylic acid. Overall, the findings of this study highlight the influence of the Bronsted and Lewis acid pairs in promoting the DMNP degradation kinetics, providing an alternative pathway to the commonly used nucleophilic substitution method.

中文翻译：

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评估用偕胺肟、醛肟和羧酸酯基团功能化的 Ce(OH)4@PIM-1 复合材料对神经毒剂模拟物 4-硝基苯基膦酸二甲酯的水解性能

近年来，人们对评估不同聚合物的反应性以测定其对危险化学品的催化活性给予了极大的关注。在这些聚合物中，PIM-1 因其显着的属性（包括高表面积、优异的溶解性以及沿着聚合物主链微调腈官能团的能力）而成为特殊的候选者。在本研究中，我们探讨了不同官能团（例如偕胺肟 (AX)、醛肟 (OX) 和羧酸酯 (COOH)）对 4-硝基苯基膦酸二甲酯 (DMNP) 降解的影响（与纯 PIM-1 和 PIM-1 相比）。它们各自的Ce(OH) ₄负载聚合物复合材料。值得注意的是，由于其高亲核性，PIM-1-AX 类似物在 24 小时内研究的官能团中表现出最高程度的催化活性（约 100%），而在 1 小时内，Ce(OH) ₄ @PIM- 1-COOH 的性能优于其他材料，其初始水解速率为 0.058 μmol/s，半衰期为 0.38 分钟，这是由于其高路易斯酸度（源于 Ce ⁴⁺与布朗斯台德羧酸的偶联）。总体而言，本研究的结果强调了布朗斯台德酸和路易斯酸对在促进 DMNP 降解动力学方面的影响，为常用的亲核取代方法提供了替代途径。