Synthesis and systematic study of Co₃O₄-based catalysts for oxygen reduction and oxygen evolution reactions

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Liu, Siyang, M.S.E.

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Co₃O₄-based composite materials are good electrocatalysts for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) in alkaline solutions. Here, this thesis first investigated the individual functionality of Co₃O₄ and the N-doped carbon nanoweb (CNW) in ORR and OER. The Co₃O₄/CNW bifunctional catalysts were synthesized by an in situ growth of Co precursors onto CNW followed by a controlled heat treatment. Rotating disk electrode measurements were utilized to provide insight into the specific functions of Co₃O₄ and CNW in the composite material during catalysis. It was found that Co₃O₄ alone exhibited poor ORR catalytic activity. However, in the presence of CNW, Co₃O₄ assisted the selective four-electron oxygen reduction over the two-electron pathway. Co₃O₄ acted as the primary catalytic site for OER and CNW improved the electronic conduction between Co₃O₄ and the current collector. CNW underwent serious degradation at the high potential of the OER, but its stability improved greatly upon the deposition of Co₃O₄. Two possible mechanisms for the improved catalytic stability are discussed. The findings demonstrate the specific functions of Co₃O₄ and CNW in catalyzing the OER and ORR and further establish an understanding of the synergy of the composite in electrocatalysis. Based on the critical functionality of Co₃O₄ in stabilizing carbon materials in the OER potential region, it is of interest to investigate novel synthesis methods to prepare nano-sized Co₃O₄ that can provide more active sites for catalytic reactions and thus, improve the OER kinetics. Here, in situ electrochemical generation of 2-dimensional Co₃O₄ (2D-Co₃O₄) nanoplates were achieved by scanning CoO[subscript x]/Co precursors in 1 M KOH solution. X-ray diffraction characterization suggested that CoO[subscript x]/Co precursors were oxidized to Co₃O₄ before the onset potential of OER. Scanning electron microscopy showed that oxidation from CoO[subscript x]/Co to 2D-Co₃O₄ was associated with the formation of hexagonal nanoplates. The 2D-Co₃O₄ exhibited excellent OER catalytic activity and stability probably due to the effective mass transfer through the 2D structure.



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