Universität zu Köln

Wenzel, Susanna (2025). Metal-Organic Frameworks (MOFs) Based on Fluorinated Trimesate Linkers. PhD thesis, Universität zu Köln.

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Abstract

This dissertation explores the preparation and characterisation of fluorinated Metal-Organic Frameworks (MOFs) incorporating zinc, copper, cobalt and indium cations. Furthermore, the influence of the degree of fluorination on the resulting structures, thermal stabilities, and sorption behaviours of these MOFs was investigated. For this purpose, stepwise fluorinated trimesate linkers derived from benzene-1,3,5-tricarboxylic acid were used. A notable highlight of this work is the synthesis of Zn-UoC-7(1F) and Zn-UoC-7(2F), which are the first anionic MOFs based on fluorinated trimesate linkers. Their crystal structures show large channels along [001], which accommodate the counter cations as well as solvent molecules. Surface areas (SBET) of 2740 m2/g (Zn-UoC7(1F)) and 1643 m2/g (Zn-UoC-7(2F)) were obtained from N2 sorption measurements. Moreover, both MOFs exhibit high CO2 uptakes, with Zn-UoC-7(2F) achieving a CO2 uptake of 247cm3/g at 273 K, which is one of the highest values reported for MOFs to date. The analysis of their thermal behaviour revealed that a higher degree of fluorination of these MOFs is likely associated with decreased thermal stability. In addition, several other anionic MOFs were successfully synthesised and analysed, including Co-UoC-7(2F), UoC-13(1F), and GaMOF-1(1F). Furthermore, the bimetallic MOFs Cu,Zn-UoC-5(1F) and Co,Zn-UoC-5(1F), featuring neutral frameworks, were structurally investigated and compared to Zn-UoC-5(1F). Their isostructural difluorinated derivatives Cu,Zn-UoC-5(2F) and Co,Zn-UoC-5(2F) were synthesised as phase-pure powders. A notable aspect of the UoC-5 structure is the presence of two SBUs: a paddlewheel unit M(COO)4 (M = Zn, Cu, Co) and an Zn4O(COO)6 unit. Furthermore, the structure possesses channels along [111] and for Cu,Zn-UoC-5(1F) and Cu,Zn-UoC-5(2F) surface areas (SBET) of 1760 m2/g (Cu,Zn-UoC-5(1F)) and 1400 m2/g (Cu,Zn-UoC5(2F)) were calculated from N2 sorption measurements, respectively.

Item Type:	Thesis (PhD thesis)
Creators:	Creators Email ORCID ORCID Put Code Wenzel, Susanna UNSPECIFIED UNSPECIFIED UNSPECIFIED
URN:	urn:nbn:de:hbz:38-742220
Date:	2025
Language:	English
Faculty:	Faculty of Mathematics and Natural Sciences
Divisions:	Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Inorganic Chemistry
Subjects:	Chemistry and allied sciences
Uncontrolled Keywords:	Keywords Language Metal-Organic Frameworks UNSPECIFIED Fluorinated Trimesate Linker UNSPECIFIED Porous Materials UNSPECIFIED
Date of oral exam:	30 October 2024
Referee:	Name Academic Title Ruschewitz, Uwe Prof. Dr.
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/74222