Covalent hybrids of graphene and metal-organic frameworks (MOFs) hold immense potential in various technologies, particularly catalysis and energy applications, due to the advantageous combination of conductivity and porosity. The formation of an amide bond between carboxylate-functionalized graphene acid (GA) and amine-functionalized UiO-66-NH2 MOF (Zr6O4(OH)4(NH2-bdc)6, with NH2-bdc2- = 2-amino-1,4-benzenedicarboxylate and UiO = Universitetet i Oslo) is a highly efficient strategy for creating such covalent hybrids. Previous experimental studies have demonstrated exceptional properties of these conductive networks, including significant surface area and functionalized hierarchical pores, showing promise as a chemiresistive CO2 sensor and electrode materials for asymmetric supercapacitors. However, the molecular-level origin of the covalent linkages between pristine MOF and GA layers remains unclear. In this study, density functional theory (DFT) calculations were conducted to elucidate the mechanism of amide bond formation between GA and UiO-66-NH2. The theoretical calculations emphasize the crucial role of zirconium within UiO-66, which acts as a catalyst in the reaction cycle. Both commonly observed hexa-coordinated and less common hepta-coordinated zirconium complexes are considered as intermediates. By gaining detailed insights into the binding interactions between graphene derivatives and MOFs, strategies for tailored syntheses of such nanocomposite materials can be developed.

Chair of Inorganic and Metal Organic Chemistry Department of Chemistry and Catalysis Research Centre Technical University of Munich 85748 Garching Germany

Hybrid Porous Materials Lab Department of Chemistry Indian Institute of Technology Jammu Jammu and Kashmir 181221 India

Institute of Organic Chemistry and Biochemistry Czech Academy of Sciences v v i Flemingovo nám 2 160 00 Prague 6 Czech Republic

IT4Innovations VŠB Technical University of Ostrava 17 listopadu 2172 15 70800 Ostrava Poruba Czech Republic

Lehrstuhl für Anorganische Chemie 1 Technische Universität Dresden Bergstr 66 01069 Dresden Germany

Nanotechnology Centre CEET VSB Technical University of Ostrava 17 listopadu 2172 15 70800 Ostrava Poruba Czech Republic

Regional Centre of Advanced Technologies and Materials Czech Advanced Technology and Research Institute Palacký University Olomouc Křížkovského 511 8 Olomouc 77900 Czech Republic

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