Creation of Exclusive Artificial Cluster Defects by Selective Metal Removal in the (Zn, Zr) Mixed-Metal UiO-66

Xiao Feng; Himanshu Sekhar Jena; Chidharth Krishnaraj; Daniel Arenas-Esteban; Karen Leus; Guangbo Wang; Jiamin Sun; Martina Rüscher; Janis Timoshenko; Beatriz Roldan Cuenya; Sara Bals; Pascal Van Der Voort

doi:10.1021/jacs.1c05357

Creation of Exclusive Artificial Cluster Defects by Selective Metal Removal in the (Zn, Zr) Mixed-Metal UiO-66

J Am Chem Soc. 2021 Dec 29;143(51):21511-21518. doi: 10.1021/jacs.1c05357. Epub 2021 Dec 7.

Authors

Affiliations

¹ Zhang Dayu School of Chemistry, State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China.
² Center for Ordered Materials, Organometallics and Catalysis (COMOC), Department of Chemistry, Ghent University, 281, Krijgslaan (S3), Ghent B-9000, Belgium.
³ Department of Physics, EMAT Electron Microscopy for Materials Science, University of Antwerp, Groenenborgerlaan 171, Antwerp 2020, Belgium.
⁴ College of Chemistry, Chemical Engineering and Materials Science, Collaborative Innovation Center of Functionalized Probes for Chemical Imaging in Universities of Shandong, Key Laboratory of Molecular and Nano Probes, Ministry for Education, Shandong Normal University, Jinan 250014, P. R. China.
⁵ Interface Science Department, Fritz-Haber Institute of the Max-Planck Society, Faradayweg 4-6, Berlin 14195, Germany.

PMID: 34872251
DOI: 10.1021/jacs.1c05357

Abstract

The differentiation between missing linker defects and missing cluster defects in MOFs is difficult, thereby limiting the ability to correlate materials properties to a specific type of defects. Herein, we present a novel and easy synthesis strategy for the creation of solely "missing cluster defects" by preparing mixed-metal (Zn, Zr)-UiO-66 followed by a gentle acid wash to remove the Zn nodes. The resulting material has the reo UiO-66 structure, typical for well-defined missing cluster defects. The missing clusters are thoroughly characterized, including low-pressure Ar-sorption, iDPC-STEM at a low dose (1.5 pA), and XANES/EXAFS analysis. We show that the missing cluster UiO-66 has a negligible number of missing linkers. We show the performance of the missing cluster UiO-66 in CO₂ sorption and heterogeneous catalysis.

Publication types

Research Support, Non-U.S. Gov't