Hydrogenation of CO on molybdenum and cobalt molybdenum carbide catalysts—Mass and infrared spectroscopy studies

Highlight
• Hydrogenation of CO on Mo and CoMo carbides by MS and infrared spectroscopies.
• C18O was dissociated and formed H218O and C18O16O.
• H2 introduction formed a significant amount of CH4 together with H216O without H218O.
• Introduction of Co to Mo2C prevented water–gas shift reaction of CO with produced H2O.

The hydrogenation of CO on Mo and CoMo carbide catalysts was evaluated by quadrupole mass (MS) and in situ infrared (FTIR) spectroscopic measurements. The difference in the catalytic properties of the Mo and CoMo carbides and the role of the Co atom in the catalytic activity were determined. The surface-adsorbed-species-derived CO and H2 were estimated using C18O for the 973 K-carburized CoMo catalyst by MS spectrometry in flowing 2%CO/61%H2 with a He balance at 453 K, showing that the C18O was dissociated to form H218O and C18O16O. The H2 introduction formed a significant amount of CH4 together with a small amount of H216O without H218O. As a result, CO was dissociatively adsorbed on the CoMo carbide by the H2 introduction to form the OH group and CH4. A slight amount of CO2 was formed during the reaction on the CoMo carbide catalyst, which was different from the formation of CO2 on the 973 K-carburized Mo catalyst. The introduction of Co to Mo2C prevented the water–gas shift reaction. The CH4 gas band at 3016 cm−1 was detected and significantly increased after the appearance of the bands for the surface OH species at 3570–3760 cm−1 on the surface of the 873 K-carburized Mo catalyst. The formation of H2O preceded the formation of CH4.

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