Experimental and theoretical investigation of molybdenum carbide and nitride as catalysts for ammonia decomposition.
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.
Department of Inorganic Chemistry, Fritz Haber Institute of the Max Planck Society, Faradayweg 4-6, 14195 Berlin, Germany.
Weiqing
W
Zheng
Thomas P
TP
Cotter
Payam
P
Kaghazchi
Timo
T
Jacob
Benjamin
B
Frank
Klaus
K
Schlichte
Wei
W
Zhang
Dang Sheng
DS
Su
Ferdi
F
Schüth
Robert
R
Schlögl
D000641:Ammonia / Q000737:chemistry*; D002384:Catalysis; D008982:Molybdenum / Q000737:chemistry*; D017672:Nitrogen Compounds / Q000737:chemistry*; D011789:Quantum Theory
D017672:Nitrogen Compounds; C574181:molybdenum carbide; D000641:Ammonia; D008982:Molybdenum