Engineering Porosity and Functionality in a Robust Twofold Interpenetrated Bismuth-Based MOF: Toward a Porous, Stable, and Photoactive Material

Wafaa A Mohamed; Jeet Chakraborty; Laurens Bourda; Roy Lavendomme; Chunhui Liu; Rino Morent; Nathalie De Geyter; Kristof Van Hecke; Anna M Kaczmarek; Pascal Van Der Voort

doi:10.1021/jacs.3c14739

Engineering Porosity and Functionality in a Robust Twofold Interpenetrated Bismuth-Based MOF: Toward a Porous, Stable, and Photoactive Material

J Am Chem Soc. 2024 May 15;146(19):13113-13125. doi: 10.1021/jacs.3c14739. Epub 2024 May 3.

Authors

Wafaa A Mohamed^{1

2}, Jeet Chakraborty¹, Laurens Bourda^{1

3}, Roy Lavendomme^{1

4}, Chunhui Liu^{1

5}, Rino Morent⁶, Nathalie De Geyter⁶, Kristof Van Hecke³, Anna M Kaczmarek⁵, Pascal Van Der Voort¹

Affiliations

¹ Center for Ordered Materials, Organometallics and Catalysis (COMOC), Department of Chemistry, Ghent University, Krijgslaan 281-S3, Ghent 9000, Belgium.
² Department of Chemistry, Faculty of Science, South Valley University, Qena 83523, Egypt.
³ XStruct, Department of Chemistry, Ghent University, Krijgslaan 281-S3, Ghent 9000, Belgium.
⁴ Laboratoire de Chimie Organique (LCO), Université libre de Bruxelles (ULB), Avenue F. D. Roosevelt 50, CP160/06, Brussels B-1050, Belgium.
⁵ NanoSensing, Department of Chemistry, Ghent University, Krijgslaan 281-S3, Ghent 9000, Belgium.
⁶ RUPT-Research Unit Plasma Technology, Department of Applied Physics, Ghent University, Sint-Pietersnieuwstraat 41-B4, Ghent 9000, Belgium.

PMID: 38700843
DOI: 10.1021/jacs.3c14739

Abstract

Defect engineering in metal-organic frameworks (MOFs) has gained worldwide research traction, as it offers tools to tune the properties of MOFs. Herein, we report a novel 2-fold interpenetrated Bi-based MOF made of a tritopic flexible organic linker, followed by missing-linker defect engineering. This procedure creates a gradually augmented micro- and mesoporosity in the parent (originally nonporous) network. The resulting MOFs can tolerate a remarkable extent of linker vacancy (with absence of up to 60% of linkers per Bi node) created by altering the crystal-growth rate as a function of synthesis temperature and duration. Owing to the enhanced porosity and availability of the uncoordinated Lewis acidic Bi sites, the defect-engineered MOFs manifested improved surface areas, augmented CO₂ and water vapor uptake, and catalytic activity. Parallel to this, the impact of defect engineering on the optoelectronic properties of these MOFs has also been studied, offering avenues for new applications.