Karve Vikram V, Schertenleib Till, Espín Jordi, Trukhina Olga, Zhang Xiyuan, Campins Marta Ximenis, Kitao Takashi, Avalos Claudia E, Uemura Takashi, Queen Wendy L
Institute of Chemical Sciences and Engineering (ISIC), École Polytechnique Fédérale de Lausanne (EPFL), CH-1051 Sion, Switzerland.
Department of Advanced Materials Science, Graduate School of Frontier Sciences, The University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8561, Japan.
ACS Appl Mater Interfaces. 2021 Dec 22;13(50):60027-60034. doi: 10.1021/acsami.1c19255. Epub 2021 Dec 13.
The number of synthetic strategies used to functionalize MOFs with polymers is rapidly growing; this stems from the knowledge that non-native polymeric guests can significantly boost MOF performance in a number of desirable applications. The current work presents a scalable and solid-state method for MOF/polymer composite production. This simple method constitutes mixing a MOF powder, namely, Fe-BTC (BTC = 1,3,5-benzenetricarboxylate), with a biomass-derived solid monomer, 5-hydroxymethylfurfural (HMF), and subsequently heating the solids; the latter promotes both solid-state diffusion of HMF into the MOF and the formation of polymeric humin species with a high density of accessible hydroxyl functionality within the MOF pore. The resulting composite, Fe-BTC/humin, was found to selectively extract Ag ions from laundry wastewater. Subsequent reduction of the Ag species yields a novel catalyst, Fe-BTC/humin/Ag, that is able to drive the organic transformation of cinnamaldehyde in a highly selective manner. Moreover, the catalyst exhibited recyclability up to five cycles, which is in contrast to the Fe-BTC/Ag catalyst without the humin-based polymer. It is envisioned that MOF/polymer composites that are able to selectively extract precious metals from liquid waste streams can be used for the future production of sustainable catalysts; this work was aimed at demonstrating a proof of concept in this regard. Moreover, this study brings more understanding of the impact that MOFs can have on polymer functionalities. Understanding the polymer structure and how it can be manipulated will help us realize the high degree of future potential of this distinct class of composite materials.
用于使金属有机框架（MOF）与聚合物功能化的合成策略数量正在迅速增加；这源于这样的认识，即非天然的聚合物客体可以在许多理想应用中显著提高MOF的性能。当前的工作提出了一种用于生产MOF/聚合物复合材料的可扩展固态方法。这种简单的方法包括将一种MOF粉末，即Fe-BTC（BTC = 1,3,5-苯三甲酸），与一种生物质衍生的固体单体5-羟甲基糠醛（HMF）混合，随后加热这些固体；后者促进了HMF在MOF中的固态扩散以及在MOF孔内形成具有高密度可及羟基官能团的聚合腐殖质物种。所得到的复合材料Fe-BTC/腐殖质被发现能够从洗衣废水中选择性地提取银离子。随后对银物种的还原产生了一种新型催化剂Fe-BTC/腐殖质/Ag，它能够以高度选择性的方式驱动肉桂醛的有机转化。此外，该催化剂表现出高达五个循环的可回收性，这与不含腐殖质基聚合物的Fe-BTC/Ag催化剂形成对比。可以设想，能够从液体废物流中选择性提取贵金属的MOF/聚合物复合材料可用于未来可持续催化剂的生产；这项工作旨在证明这方面的概念验证。此外，这项研究使人们对MOF对聚合物功能的影响有了更多的了解。了解聚合物结构及其如何被调控将有助于我们认识到这类独特复合材料未来的巨大潜力。
