共价键
石墨烯
催化作用
酰胺
化学
锆
路易斯酸
组合化学
密度泛函理论
材料科学
金属有机骨架
纳米技术
计算化学
有机化学
吸附
作者
Rabindranath Lo,Martin Pykal,Andreas Schneemann,Radek Zbořil,Roland A. Fischer,Kolleboyina Jayaramulu,Michal Otyepka
标识
DOI:10.1021/acs.jpcc.3c01821
摘要
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.
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