Liang Rong-Ran, Xu Shunqi, Han Zongsu, Yang Yihao, Wang Kun-Yu, Huang Zhehao, Rushlow Joshua, Cai Peiyu, Samorì Paolo, Zhou Hong-Cai
Department of Chemistry, Texas A&M University, College Station, Texas 77843, United States.
Université de Strasbourg, CNRS, ISIS, 8 alleé Gaspard Monge, 67000 Strasbourg, France.
J Am Chem Soc. 2024 Apr 10;146(14):9811-9818. doi: 10.1021/jacs.3c14487. Epub 2024 Mar 26.
Perfluorooctanoic acid (PFOA) is an environmental contaminant ubiquitous in water resources, which as a xenobiotic and carcinogenic agent, severely endangers human health. The development of techniques for its efficient removal is therefore highly sought after. Herein, we demonstrate an unprecedented zirconium-based MOF (PCN-999) possessing Zr and biformate-bridged (Zr) clusters simultaneously, which exhibits an exceptional PFOA uptake of 1089 mg/g (2.63 mmol/g), representing a ca. 50% increase over the previous record for MOFs. Single-crystal X-ray diffraction studies and computational analysis revealed that the (Zr) clusters offer additional open coordination sites for hosting PFOA. The coordinated PFOAs further enhance the interaction between coordinated and free PFOAs for physical adsorption, boosting the adsorption capacity to an unparalleled high standard. Our findings represent a major step forward in the fundamental understanding of the MOF-based PFOA removal mechanism, paving the way toward the rational design of next-generation adsorbents for per- and polyfluoroalkyl substance (PFAS) removal.
全氟辛酸（PFOA）是一种普遍存在于水资源中的环境污染物，作为一种外源性致癌物质，严重危害人类健康。因此，高效去除PFOA的技术备受关注。在此，我们展示了一种前所未有的基于锆的金属有机框架（PCN-999），它同时拥有锆和双甲酸桥连（Zr）簇，对PFOA的吸附量高达1089 mg/g（2.63 mmol/g），比之前金属有机框架的记录提高了约50%。单晶X射线衍射研究和计算分析表明，（Zr）簇为容纳PFOA提供了额外的开放配位位点。配位的PFOA进一步增强了配位态和游离态PFOA之间的相互作用，从而促进物理吸附，将吸附容量提升至无与伦比的高标准。我们的研究结果在基于金属有机框架的PFOA去除机制的基础理解方面迈出了重要一步，为合理设计下一代用于去除全氟和多氟烷基物质（PFAS）的吸附剂铺平了道路。
