Prasad Ram R R, Boyadjieva Sophia S, Zhou Guojun, Tan Jiangtian, Firth Francesca C N, Ling Sanliang, Huang Zhehao, Cliffe Matthew J, Foster Jonathan A, Forgan Ross S
Department of Chemistry, The University of Sheffield, Sheffield S3 7HF, U.K.
WestCHEM School of Chemistry, University of Glasgow, Joseph Black Building, University Avenue, Glasgow G12 8QQ, U.K.
ACS Appl Mater Interfaces. 2024 Apr 10;16(14):17812-17820. doi: 10.1021/acsami.4c00604. Epub 2024 Apr 1.
Two-dimensional metal-organic nanosheets (MONs) have emerged as attractive alternatives to their three-dimensional metal-organic framework (MOF) counterparts for heterogeneous catalysis due to their greater external surface areas and higher accessibility of catalytically active sites. Zr MONs are particularly prized because of their chemical stability and high Lewis and Brønsted acidities of the Zr clusters. Herein, we show that careful control over modulated self-assembly and exfoliation conditions allows the isolation of the first example of a two-dimensional nanosheet wherein Zr clusters are linked by dicarboxylate ligands. The topology MOF, termed GUF-14 (GUF = Glasgow University Framework), can be exfoliated into monolayer thickness topology MONs, and acid-induced removal of capping modulator units yields MONs with enhanced catalytic activity toward the formation of imines and the hydrolysis of an organophosphate nerve agent mimic. The discovery of GUF-14 serves as a valuable example of the undiscovered MOF/MON structural diversity extant in established metal-ligand systems that can be accessed by harnessing the power of modulated self-assembly protocols.
二维金属有机纳米片（MONs）作为其三维金属有机框架（MOF）对应物在多相催化中的有吸引力的替代物而出现，这是由于它们具有更大的外表面面积和更高的催化活性位点可及性。Zr MONs因其化学稳定性以及Zr簇的高路易斯酸度和布朗斯特酸度而特别受重视。在此，我们表明，对调制自组装和剥离条件进行仔细控制，可以分离出二维纳米片的首个实例，其中Zr簇通过二羧酸酯配体连接。拓扑MOF，称为GUF-14（GUF = 格拉斯哥大学框架），可以剥离成单层厚度的拓扑MONs，并且酸诱导去除封端调节剂单元会产生对亚胺形成和有机磷酸酯神经毒剂模拟物水解具有增强催化活性的MONs。GUF-14的发现是一个有价值的例子，说明在已建立的金属-配体体系中存在尚未发现的MOF/MON结构多样性，通过利用调制自组装方案的力量可以获得这些多样性。
