Department of Chemistry, Rice University, Houston, Texas 77005, United States.
Laboratory of Nanophotonics, Rice University, Houston, Texas 77005, United States.
Nano Lett. 2022 Sep 28;22(18):7699-7705. doi: 10.1021/acs.nanolett.2c03188. Epub 2022 Sep 8.
Plasmonic nanostructures have attracted increasing interest in the fields of photochemistry and photocatalysis for their ability to enhance reactivity and tune reaction selectivity, a benefit of their strong interactions with light and their multiple energy decay mechanisms. Here we introduce the use of earth-abundant plasmonic aluminum nanoparticles as a promising renewable detoxifier of the sulfur mustard simulant 2-chloroethylethylsulfide through gas phase photodecomposition. Analysis of the decomposition products indicates that C-S bond breaking is facilitated under illumination, while C-Cl breaking and HCl elimination are favored under thermocatalytic (dark) conditions. This difference in reaction pathways illuminates the potential of plasmonic nanoparticles to tailor reaction selectivity toward less hazardous products in the detoxification of chemical warfare agents. Moreover, the photocatalytic activity of the Al nanoparticles can be regenerated almost completely after the reaction concludes through a simple surface treatment.
等离子体纳米结构因其能够增强反应活性和调节反应选择性而在光化学和光催化领域引起了越来越多的关注，这得益于它们与光的强相互作用和多种能量衰减机制。在这里，我们介绍了使用丰富的等离子体铝纳米颗粒作为 2-氯乙基乙基硫模拟物的有前途的可再生解毒剂，通过气相光分解来实现。对分解产物的分析表明，在光照下 C-S 键的断裂得到促进，而在热催化（黑暗）条件下 C-Cl 的断裂和 HCl 的消除则更有利。这种反应途径的差异说明了等离子体纳米颗粒在化学战剂解毒中为更危险产物的反应选择性定制的潜力。此外，通过简单的表面处理，反应结束后，Al 纳米颗粒的光催化活性几乎可以完全再生。
