Item

Abstract

Constant CO_x-free H₂ production from the catalytic decomposition of ammonia could be achieved over a high-surface-area molybdenum carbide catalyst prepared by a temperature-programmed reduction–carburization method. The fresh and used catalyst was characterized by N₂ adsorption/desorption, powder X-ray diffraction, scanning and transmission electron microscopy, and electron energy-loss spectroscopy at different stages. Observed deactivation (in the first 15 h) of the high-surface-area carbide during the reaction was ascribed to considerable reduction of the specific surface area due to nitridation of the carbide under the reaction conditions. Theoretical calculations confirm that the N atoms tend to occupy subsurface sites, leading to the formation of nitride under an NH₃ atmosphere. The relatively high rate of reaction (30 mmol/((g of cat.) min)) observed for the catalytic decomposition of NH₃ is ascribed to highly energetic sites (twin boundaries, stacking faults, steps, and defects) which are observed in both the molybdenum carbide and nitride samples. The prevalence of such sites in the as-synthesized material results in a much higher H₂ production rate in comparison with that for previously reported Mo-based catalysts.