Decomposition of N₂O on ZIF-67-Derived Co/CoO_x@Carbon Catalysts and SO₂ Interference

Abstract

Zeolitic-imidazolate framework precursors (ZIF-67) were synthesized in an inorganic solution with triethylamine as a deprotonating agent for N2O decomposition, and the catalytic activities of the pyrolysis products under different conditions were investigated. Among them, the Co/CoO x @carbon catalyst pyrolyzed at 650 °C in a N2 atmosphere (Co-650N) exhibited excellent low-temperature catalytic activity and stability, achieving 50% decomposition efficiency at 305 °C and ∼100% at 400 °C, which benefitted from its large specific surface area, great reduction performance, abundant cobalt active sites, and surface oxygen species. Further, utilizing temperature-programmed desorption (TPD) and in situ diffused reflectance infrared Fourier transform spectroscopy (DRIFTS) results, it was found that N2O molecules preferentially combined with oxygen species bound to cobalt sites. The absorbed N2O was decomposed into N2 and oxygen species, and the latter was subsequently transferred to carbon frameworks. Interestingly, the amorphous graphitic carbon frameworks played an important role in transferring/storing active oxygen and regenerating cobalt sites. Moreover, Co-650N exhibited better resistance to SO2, and the efficiency could be recovered via heating and finally stabilized at 100%. Finally, the mechanisms of N2O decomposition and sulfur poisoning-reactivation on Co/CoO x @carbon catalysts were proposed for the first time.