Nowadays, it is still elusive and
challenging to discover the active
sites of cobalt (Co) cations in different coordination structures,
though Co-based oxides show their great potency in catalytic ozone
elimination for air cleaning. Herein, different Co-based oxides are
controllably synthesized including hexagonal wurtzite CoO-W with Co2+ in tetrahedral coordination (CoTd
2+) and CoAl spinel with dominant CoTd
2+, cubic
rock salt CoO-R with Co2+ in octahedral coordination (CoOh
2+), MgCo spinel with dominant Co3+ in octahedral coordination (CoOh
3+), and Co3O4 with mixed CoTd
2+ and
CoOh
3+. The valences are proved by X-ray photoelectron
spectroscopy, and the coordinations are verified by X-ray absorption
fine structure analysis. The ozone decomposition performances are
CoOh
3+ ∼ CoOh
2+ ≫ CoTd
2+, and CoOh
3+ and CoOh
2+ show a lower apparent activation
energy of ∼42–44 kJ/mol than CoTd
2+ (∼55 kJ/mol). In specific, MgCo shows the highest decomposition
efficiency of 95% toward 100 ppm ozone at a high space velocity of
1,200,000 mL/gh, which still retains at 80% after a long-term running
of 36 h at room temperature. The high activity is explained by the
d-orbital splitting in the octahedral coordination, favoring the electron
transfer in ozone decomposition reactions, which is also verified
by the simulation. These results show the promising prospect of the
coordination tuning of Co-based oxides for highly active ozone decomposition
catalysts.