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Oxygen Vacancy-Determined Highly Efficient Oxygen Reduction in NiCo 2 O 4 /Hollow Carbon Spheres.
ACS Applied Materials & Interfaces 2018 May 17
Rationally generating oxygen vacancies in electrocatalysts is an important approach to modulate the electrochemical activity of a catalyst. Herein, we report a remarkable enhancement in oxygen reduction reaction (ORR) activity of NiCo2 O4 supported on hollow carbon spheres (HCS) achieved through generating abundant oxygen vacancies within the surface lattice. This catalyst exhibits enhanced ORR activity (larger limiting current density of ∼-5.8 mA cm-2 ) and higher stability (∼90% retention after 40 000 s) compared with those of NiCo2 O4 /HCS and NiCo2 O4 . The results of X-ray photoelectron spectroscopy (XPS) characterizations suggest that the introduction of oxygen vacancies optimizes the valence state of active sites. Furthermore, we carried out density functional theory (DFT) calculations to further confirm the mechanism of oxygen vacancies, and results show that oxygen vacancies enhance the density of states (DOS) near the Fermi level, decrease work function, and lower the calculated overpotential of NiCo2 O4 .
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