In this work, the covalent attachment of an amine functionalized metal-organic framework (UiO-66-NH2 = Zr6 O4 (OH)4 (bdc-NH2 )6 ; bdc-NH2 = 2-amino-1,4-benzenedicarboxylate) (UiO-Universitetet i Oslo) to the basal-plane of carboxylate functionalized graphene (graphene acid = GA) via amide bonds is reported. The resultant GA@UiO-66-NH2 hybrid displayed a large specific surface area, hierarchical pores and an interconnected conductive network. The electrochemical characterizations demonstrated that the hybrid GA@UiO-66-NH2 acts as an effective charge storing material with a capacitance of up to 651 F g-1 , significantly higher than traditional graphene-based materials. The results suggest that the amide linkage plays a key role in the formation of a π-conjugated structure, which facilitates charge transfer and consequently offers good capacitance and cycling stability. Furthermore, to realize the practical feasibility, an asymmetric supercapacitor using a GA@UiO-66-NH2 positive electrode with Ti3 C2 TX MXene as the opposing electrode has been constructed. The cell is able to deliver a power density of up to 16 kW kg-1 and an energy density of up to 73 Wh kg-1 , which are comparable to several commercial devices such as Pb-acid and Ni/MH batteries. Under an intermediate level of loading, the device retained 88% of its initial capacitance after 10 000 cycles.

Adam Mickiewicz University in Poznań NanoBioMedical Centre Wszechnicy Piastowskiej 3 Poznań PL61614 Poland

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

Chemistry and Physics of Materials Unit Jawaharlal Nehru Centre for Advanced Scientific Research Jakkur Bangalore 560064 India

Department of Chemistry Indian Institute of Technology Jammu Nagrota Jammu and Kashmir 181221 India

Inorganic Chemistry Department of Chemistry and Food Chemistry Technische Universität Dresden Bergstr 66 Dresden 01069 Germany

Nanotechnology Centre VŠB Technical University of Ostrava 17 listopadu 2172 15 Ostrava Poruba 708 00 Czech Republic

Regional Centre of Advanced Technologies and Materials Faculty of Science Palacky University Šlechtitelů 27 Olomouc 78371 Czech Republic

Sandia National Laboratories 7011 East Avenue MS9161 Livermore CA 94550 USA

School of Chemistry and Physics Queensland University of Technology 2 George Street Brisbane QLD 4001 Australia

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Lewis Acid Catalyzed Amide Bond Formation in Covalent Graphene-MOF Hybrids

Graphene-Based Metal-Organic Framework Hybrids for Applications in Catalysis, Environmental, and Energy Technologies