Abazari Reza, Sanati Soheila, Morsali Ali, Slawin Alexandra, L Carpenter-Warren Cameron
Department of Chemistry , Tarbiat Modares University , P.O. Box 14115-175, Tehran , Iran.
EaStCHEM, School of Chemistry , University of St Andrews , St Andrews, Fife KY16 9ST , Scotland , U.K.
ACS Appl Mater Interfaces. 2019 Apr 24;11(16):14759-14773. doi: 10.1021/acsami.9b00415. Epub 2019 Apr 10.
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)(4-bpdb)] (2-ATA: 2-aminoterephthalic acid and 4-bpdb: N, N-bis-pyridin-4-ylmethylene-hydrazine as the pillar spacer), which is called NH-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 HO as an oxidant enhances the efficiency of sulfur removal, which indicates that NH-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 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, NH-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 at 5 A g current density. The asymmetric supercapacitor of NH-TMU-53//activated carbon evaluates the further electrochemical activity in real applications, delivers the high power density (2.31 kW kg), high energy density (50.30 Wh kg), 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.
本研究提出了一种方法，用于在温和反应条件下改善柴油的氧化脱硫（ODS）催化作用，并增强超级电容器（SC）存储大量电荷的性能。我们的方法利用了一种新型的基于钴（II）的双功能金属有机框架（MOF），即[Co(2-ATA)(4-bpdb)]（2-ATA：2-氨基对苯二甲酸，4-bpdb：N，N-双吡啶-4-基亚甲基肼作为支柱间隔物），其被称为NH-TMU-53。由于所用化合物的稳定性，我们决定评估该化合物作为超级电容器中存储能量的新型电极材料的能力，并研究其催化能力。结果表明，添加H₂O₂作为氧化剂可提高脱硫效率，这表明NH-TMU-53可以有效地催化ODS反应。根据动力学结果，催化过程遵循准一级动力学，表现出15.57 kJ mol的活化能。此外，关于自由基清除评估，该过程由直接催化氧化而非自由基的间接氧化攻击控制。此外，NH-TMU-53被用作SC中能量存储的电极材料。该材料用于三电极系统，在5 A g电流密度下显示出325 F g的比电容。NH-TMU-53//活性炭的不对称超级电容器评估了其在实际应用中的进一步电化学活性，具有高功率密度（2.31 kW kg）、高能量密度（50.30 Wh kg）以及6000次循环后的长循环寿命（90.7%）。此外，通过发红光的发光二极管和驱动微型旋转电机展示了不对称超级电容器的实际应用。这些结果表明，所制备的器件在不热解MOF结构的情况下具有良好的能量存储能力。这些发现可以引导高性能SCs朝着改善其实际应用的新方向发展，并推动无需热解或煅烧的MOFs的应用。
