▎ 摘　　要

Covalent hybrids of graphene and metal-organicframeworks(MOFs) hold immense potential in various technologies, particularlycatalysis and energy applications, due to the advantageous combinationof conductivity and porosity. The formation of an amide bond betweencarboxylate-functionalized graphene acid (GA) and amine-functionalizedUiO-66-NH2 MOF (Zr6O4(OH)(4)(NH2-bdc)(6), with NH2-bdc(2-) = 2-amino-1,4-benzene-dicarboxylate and UiO = Universiteteti Oslo) is a highly efficient strategy for creating such covalenthybrids. Previous experimental studies have demonstrated exceptionalproperties of these conductive networks, including significant surfacearea and functionalized hierarchical pores, showing promise as a chemiresistiveCO(2) sensor and electrode materials for asymmetric supercapacitors.However, the molecular-level origin of the covalent linkages betweenpristine MOF and GA layers remains unclear. In this study, densityfunctional theory (DFT) calculations were conducted to elucidate themechanism of amide bond formation between GA and UiO-66-NH2. The theoretical calculations emphasize the crucial role of zirconiumwithin UiO-66, which acts as a catalyst in the reaction cycle. Bothcommonly observed hexa-coordinated and less common hepta-coordinatedzirconium complexes are considered as intermediates. By gaining detailedinsights into the binding interactions between graphene derivativesand MOFs, strategies for tailored syntheses of such nanocompositematerials can be developed.