Dual-Purpose 3D Pillared Metal-Organic Framework with Excellent Properties for Catalysis of Oxidative Desulfurization and Energy Storage in Asymmetric Supercapacitor.

Abstract

This study proposes an approach for improving catalysis of oxidative desulfurization (ODS) of diesel fuel under mild reaction conditions and enhancing supercapacitor (SC) properties for storage of a high amount of charge. Our approach takes advantage of a novel dual-purpose cobalt(II)-based metal-organic framework (MOF), [Co(2-ATA)2(4-bpdb)4] n (2-ATA: 2-aminoterephthalic acid and 4-bpdb: N, N-bis-pyridin-4-ylmethylene-hydrazine as the pillar spacer), which is called NH2-TMU-53. Due to the stability of the used compound, we decided to evaluate the capability of this compound as a novel electrode material for storing energy in supercapacitors, and also to investigate its catalytic capabilities. It is demonstrated that the addition of H2O2 as an oxidant enhances the efficiency of sulfur removal, which indicates that NH2-TMU-53 can efficiently catalyze the ODS reaction. According to the kinetics results, the catalyzed process follows pseudo-first-order kinetics and exhibits 15.57 kJ mol-1 activation energy. Moreover, with respect to the radical scavenging evaluations, the process is governed by direct catalytic oxidation rather than indirect oxidative attack of radicals. Furthermore, NH2-TMU-53 was applied as an electrode material for energy storage in SCs. This material is used in the three-electrode system and shows a specific capacitance of 325 F g-1 at 5 A g-1 current density. The asymmetric supercapacitor of NH2-TMU-53//activated carbon evaluates the further electrochemical activity in real applications, delivers the high power density (2.31 kW kg-1), high energy density (50.30 Wh kg-1), and long cycle life after 6000 cycles (90.7%). Also, the asymmetric supercapacitor practical application was demonstrated by a glowing red light-emitting diode and driving a mini-rotating motor. These results demonstrate that the fabricated device presents a good capacity for energy storage without pyrolyzing the MOF structures. These findings can guide the development of high-performance SCs toward a new direction to improve their practical applications and motivate application of MOFs without pyrolysis or calcination.