Grissom Tyler G, Plonka Anna M, Sharp Conor H, Ebrahim Amani M, Tian Yiyao, Collins-Wildman Daniel L, Kaledin Alexey L, Siegal Harrison J, Troya Diego, Hill Craig L, Frenkel Anatoly I, Musaev Djamaladdin G, Gordon Wesley O, Karwacki Christopher J, Mitchell Mark B, Morris John R
Department of Chemistry, Virginia Tech, Blacksburg, Virginia 24061, United States.
Department of Materials Science and Chemical Engineering, Stony Brook University, Stony Brook, New York 11794, United States.
ACS Appl Mater Interfaces. 2020 Apr 1;12(13):14641-14661. doi: 10.1021/acsami.9b20833. Epub 2020 Jan 29.
The threat of chemical warfare agents (CWAs), assured by their ease of synthesis and effectiveness as a terrorizing weapon, will persist long after the once-tremendous stockpiles in the U.S. and elsewhere are finally destroyed. As such, soldier and civilian protection, battlefield decontamination, and environmental remediation from CWAs remain top national security priorities. New chemical approaches for the fast and complete destruction of CWAs have been an active field of research for many decades, and new technologies have generated immense interest. In particular, our research team and others have shown metal-organic frameworks (MOFs) and polyoxometalates (POMs) to be active for sequestering CWAs and even catalyzing the rapid hydrolysis of agents. In this Forum Article, we highlight recent advancements made in the understanding and evaluation of POMs and Zr-based MOFs as CWA decontamination materials. Specifically, our aim is to bridge the gap between controlled, solution-phase laboratory studies and real-world or battlefield-like conditions by examining agent-material interactions at the gas-solid interface utilizing a multimodal experimental and computational approach. Herein, we report our progress in addressing the following research goals: (1) elucidating molecular-level mechanisms of the adsorption, diffusion, and reaction of CWA and CWA simulants within a series of Zr-based MOFs, such as UiO-66, MOF-808, and NU-1000, and POMs, including CsNbO and (EtNH)[(α-PWOZr(μ-OH)(HO))]·7HO, (2) probing the effects that common ambient gases, such as CO, SO, and NO, have on the efficacy of the MOF and POM materials for CWA destruction, and (3) using CWA simulant results to develop hypotheses for live agent chemistry. Key hypotheses are then tested with targeted live agent studies. Overall, our collaborative effort has provided insight into the fundamental aspects of agent-material interactions and revealed strategies for new catalyst development.
化学战剂（CWAs）因其易于合成且作为恐怖武器效果显著而构成威胁，即便美国及其他地区曾经数量巨大的库存最终被销毁，这种威胁仍将长期存在。因此，保护士兵和平民、进行战场去污以及对化学战剂进行环境修复仍是国家安全的首要任务。数十年来，用于快速、彻底销毁化学战剂的新化学方法一直是一个活跃的研究领域，新技术引发了极大的兴趣。特别是，我们的研究团队及其他团队已表明金属有机框架（MOFs）和多金属氧酸盐（POMs）对隔离化学战剂甚至催化战剂的快速水解具有活性。在这篇论坛文章中，我们重点介绍了在理解和评估多金属氧酸盐及锆基金属有机框架作为化学战剂去污材料方面取得的最新进展。具体而言，我们的目标是通过采用多模态实验和计算方法研究气 - 固界面处的战剂 - 材料相互作用，弥合可控的溶液相实验室研究与实际或类似战场条件之间的差距。在此，我们报告在实现以下研究目标方面取得的进展：（1）阐明一系列锆基金属有机框架（如UiO - 66、MOF - 808和NU - 1000）以及多金属氧酸盐（包括CsNbO和(EtNH)[(α - PWOZr(μ - OH)(HO))]·7HO）中化学战剂及其模拟物的吸附、扩散和反应的分子水平机制；（2）探究常见环境气体（如CO、SO和NO）对金属有机框架和多金属氧酸盐材料销毁化学战剂功效的影响；（3）利用化学战剂模拟物的研究结果为实际战剂化学提出假设。然后通过有针对性的实际战剂研究对关键假设进行检验。总体而言，我们的合作努力为战剂 - 材料相互作用的基本方面提供了见解，并揭示了新催化剂开发的策略。
