Modulated Self-Assembly of Catalytically Active Metal-Organic Nanosheets Containing Zr6 Clusters and Dicarboxylate Ligands

Ram R R Prasad; Sophia S Boyadjieva; Guojun Zhou; Jiangtian Tan; Francesca C N Firth; Sanliang Ling; Zhehao Huang; Matthew J Cliffe; Jonathan A Foster; Ross S Forgan

doi:10.1021/acsami.4c00604

Modulated Self-Assembly of Catalytically Active Metal-Organic Nanosheets Containing Zr₆ Clusters and Dicarboxylate Ligands

ACS Appl Mater Interfaces. 2024 Apr 10;16(14):17812-17820. doi: 10.1021/acsami.4c00604. Epub 2024 Apr 1.

Authors

Affiliations

¹ Department of Chemistry, The University of Sheffield, Sheffield S3 7HF, U.K.
² WestCHEM School of Chemistry, University of Glasgow, Joseph Black Building, University Avenue, Glasgow G12 8QQ, U.K.
³ Department of Materials and Environmental Chemistry, Stockholm University, Stockholm SE-10691, Sweden.
⁴ Yusuf Hamied Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, U.K.
⁵ Advanced Materials Research Group, Faculty of Engineering, University of Nottingham, University Park, Nottingham NG7 2RD, U.K.
⁶ School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, U.K.

Abstract

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 Zr₆ clusters are linked by dicarboxylate ligands. The hxl topology MOF, termed GUF-14 (GUF = Glasgow University Framework), can be exfoliated into monolayer thickness hns 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.

Keywords: catalysis; coordination modulation; detoxification; metal−organic frameworks; nanosheets; nerve agents; organophosphorus compounds; two-dimensional materials.