4.7 Article

NiCo2O4 spinel supported N-dopped porous Hollow carbon derived MOF functionalized SiO2 for efficient ORR electrocatalysis

Journal

INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
Volume 48, Issue 49, Pages 18890-18905

Publisher

PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.ijhydene.2023.02.024

Keywords

Metal oxide spinel; ORR; Metal-organic frameworks (MOFs); NH2-MIL-125

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In order to achieve large-scale commercial applications of fuel cells, the development of environmentally friendly, cost-effective, and highly durable metal-free carbon-based electrocatalysts for the cathodic ORR is required. Researchers developed TiO2 nanoparticles supported by a nitrogen-doped carbon matrix derived from the pyrolysis of NH2-MIL-125 (MOF), with controllable morphology, porosity, and particle size achieved through the introduction of a SiO2 template. The synergic covalent coupling between metal oxide spinel (AB2O4, particularly NiCo2O4) and TiO2/N-doped nanocarbon effectively enhanced the ORR catalytic activity.
The improvement of carbon-based metal-free electrocatalysts for the cathodic ORR that are environmentally benign, cost-effective, and highly durable is required for large-scale commercial applications of fuel cells. Herein, we developed the TiO2 nanoparticles sup-ported by a nitrogen-doped carbon matrix with high surface defects derived by the py-rolysis of NH2-MIL-125 (MOF). The construction of controllable morphology, porosity, and particle size through the pyrolysis process can be obtained by introducing the SiO2 tem-plate during the NH2-MIL-125 synthesis. Moreover, the synergic covalent coupling between metal oxide spinel (AB2O4, especially NiCo2O4) and TiO2/N-doped nanocarbon effectively enhanced the ORR catalytic activity, particularly with high content of nickel atoms in the spinel due to the various valences of metals in spinel which accelerated the electron transfer during ORR. As a highly effective ORR electrocatalyst with an onset potential of-0.14 V vs Ag/AgCl, the as-prepared N3CO/Es-TiO2/NC exhibited not only high activity but also good stability in an alkaline environment compared to the Pt/C catalyst. The less current change after continuous 1000 cycles of cyclic voltammetry or the methanol addi-tion may be due to the protective effect of the N-doped carbon carrier and the corrosion resistance of TiO2. (c) 2023 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

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