Liang Rong-Ran, Yang Yihao, Han Zongsu, Bakhmutov Vladimir I, Rushlow Joshua, Fu Yubin, Wang Kun-Yu, Zhou Hong-Cai
Department of Chemistry, Texas A&M University, College Station, TX, 77843, USA.
Center for Advancing Electronics Dresden (cfaed) & Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, Mommsenstrasse 4, 01062, Dresden, Germany.
Adv Mater. 2024 Aug;36(33):e2407194. doi: 10.1002/adma.202407194. Epub 2024 Jun 26.
Perfluorooctanoic acid (PFOA) is a highly recalcitrant organic pollutant, and its bioaccumulation severely endangers human health. While various methods are developed for PFOA removal, the targeted design of adsorbents with high efficiency and reusability remains largely unexplored. Here the rational design and synthesis of two novel zirconium-based metal‒organic frameworks (MOFs) bearing free ortho-hydroxy sites, namely noninterpenetrated PCN-1001 and twofold interpenetrated PCN-1002, are presented. Single crystal analysis of the pure ligand reveals that intramolecular hydrogen bonding plays a pivotal role in directing the formation of MOFs with free hydroxy groups. Furthermore, the transformation from PCN-1001 to PCN-1002 is realized. Compared to PCN-1001, PCN-1002 displays higher chemical stability due to interpenetration, thereby demonstrating an exceptional PFOA adsorption capacity of up to 632 mg g (1.53 mmol g), which is comparable to the reported record values. Moreover, PCN-1002 shows rapid kinetics, high selectivity, and long-life cycles in PFOA removal tests. Solid-state nuclear magnetic resonance results and density functional theory calculations reveal that multiple hydrogen bonds between the free ortho-hydroxy sites and PFOA, along with Lewis acid-base interaction, work collaboratively to enhance PFOA adsorption.
全氟辛酸（PFOA）是一种极难降解的有机污染物，其生物累积性严重危害人类健康。尽管已开发出多种去除PFOA的方法，但具有高效性和可重复使用性的吸附剂的靶向设计在很大程度上仍未得到探索。本文介绍了两种新型的带有游离邻羟基的锆基金属有机框架材料（MOF）的合理设计与合成，即非互穿的PCN - 1001和二重互穿的PCN - 1002。对纯配体的单晶分析表明，分子内氢键在引导具有游离羟基的MOF的形成中起关键作用。此外，实现了从PCN - 1001到PCN - 1002的转变。与PCN - 1001相比，PCN - 1002由于互穿作用而表现出更高的化学稳定性，从而展现出高达632 mg g（1.53 mmol g）的出色PFOA吸附容量，这与已报道的记录值相当。此外，PCN - 1002在PFOA去除测试中显示出快速的动力学、高选择性和长寿命周期。固态核磁共振结果和密度泛函理论计算表明，游离邻羟基位点与PFOA之间的多个氢键以及路易斯酸碱相互作用协同作用，增强了PFOA的吸附。
