Developing effective catalysts for N2O decomposition at low temperatures is challenging. Herein, the Cs-O-Co structure, as the active species fabricated by single-layer atoms of Cs over pure Co3O4, originally exhibited great catalytic activity of N2O decomposition in simulated vehicle exhaust and flue gas from nitric acid plants. A similar catalytic performance was also observed for Na, K, and Rb alkali metals over Co3O4 catalysts for N2O decomposition, illustrating the prevalence of alkali-metal-promotion over Co3O4 in practical applications. The catalytic results indicated that the TOF of Co3O4 catalysts loaded by 4 wt% Cs was nearly 2 orders of magnitude higher than that of pure Co3O4 catalysts at 300 °C. Interestingly, the conversions of N2O decomposition over Co3O4 catalysts doped by the same Cs loadings were significantly inhibited. Characterization results indicated that the primary active Cs-O-Co structure was formed by highly orbital hybridization between the Cs 6s and the O 2p orbital over the supported Co3O4 catalysts, where Cs could donate electrons to Co3+ and produce much more Co2+. In contrast, the doped Co3O4 catalysts were dominated by Cs2O2 species; meanwhile, CsOH species was generated by adsorbed water vapor led to a significant decrease in catalytic activity. In situ DRIFTS, rigorous kinetics, and DFT results elaborated the reaction mechanism of N2O decomposition, where the direct decomposition of adsorbed N2O was the kinetically relevant step over supported catalysts in the absence of O2. Meanwhile, the assistance of adsorbed N2O decomposition by activated oxygen was observed as the kinetically relevant step in the presence of O2. The results may pave a promising path toward developing alkali-metal-promotion catalysts for efficient N2O decomposition.
Keywords: N2O removal; alkali-metal-promotion; catalytic decomposition; cobalt catalysts; greenhouse gas.