Taming the Redox Property of A_0.5Co_2.5O₄ (A = Mg, Ca, Sr, Ba) toward High Catalytic Activity for N₂O Decomposition

Nitrous oxide (N2O) originating from the combustion of fossil fuels causes serious environmental issues. The design and construction of a catalyst with high performance for the removal of N2O remains challenging. Herein, a series of alkaline-earth metal-modified A0.5Co2.5O4 (A = Mg, Ca, Sr, Ba) catalysts were initiated by a hydrothermal protocol, and their catalytic activities for N2O decomposition were systematically investigated by experimental and density functional theory calculation. The results reveal that the doping of alkaline-earth metals significantly affects the morphology, structure, active oxygen species, oxygen vacancy, and redox property and thereafter the catalytic activity of A0.5Co2.5O4 for N2O catalytic decomposition. The introduction of alkaline-earth metals (A = Ca, Sr, Ba) considerably promoted the reduction of Co3+ to Co2+, thereby improving the electron-donating ability and oxygen vacancy number and thereafter weakening the Co–O bond. As a result, the catalytic activity of N2O decomposition distinctively enhanced. Among them, Ba0.5Co2.5O4 shows optimal N2O decomposition performance by virtue of its outstanding active oxygen species and excellent redox property. However, the doping of Mg suppresses the electron-donating ability of Mg0.5Co2.5O4 and thereafter the catalytic activity for N2O decomposition. Therefore, this work may shine light on the understanding of N2O decomposition over alkaline-earth metal-modified Co-based oxides.