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

Reza Abazari; Soheila Sanati; Ali Morsali; Alexandra Slawin; Cameron L Carpenter-Warren

doi:10.1021/acsami.9b00415

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

ACS Appl Mater Interfaces. 2019 Apr 24;11(16):14759-14773. doi: 10.1021/acsami.9b00415. Epub 2019 Apr 10.

Authors

Reza Abazari¹, Soheila Sanati¹, Ali Morsali¹, Alexandra Slawin², Cameron L Carpenter-Warren²

Affiliations

¹ Department of Chemistry , Tarbiat Modares University , P.O. Box 14115-175, Tehran , Iran.
² EaStCHEM, School of Chemistry , University of St Andrews , St Andrews, Fife KY16 9ST , Scotland , U.K.

PMID: 30924640
DOI: 10.1021/acsami.9b00415

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.

Keywords: asymmetric supercapacitor; cyclic stability; electrode material; metal−organic framework; oxidative desulfurization; without pyrolysis.