In Situ Raman Spectroscopy of H₂ Gas Interaction with Layered MoO₃

Abstract

It is known that the unique layered structure of orthorhombic MoO3 (α-MoO3) facilitates the interaction with H2 gas molecules and that the surface-to-volume ratios of the crystallites play an important role in the process. MoO3 was deposited on a wide variety of transparent substrates using thermal evaporation in order to alter the surface-to-volume ratios of the crystallites. In situ Raman spectroscopy was employed to investigate the interaction between MoO3 and 1% H2 in both N2 and synthetic air environments, while incorporating Pd as a catalyst at room temperature. This study confirmed that the layered MoO3 with a high surface-to-volume ratio facilitated the H2 gas interaction. The Raman spectroscopy studies revealed that the H+ ions mainly interacted with the doubly coordinated oxygen atoms and caused the crystal transformation from the original α-MoO3 into the mixed structure of hydrogen molybdenum bronze and substoichiometric MoO3, eventually forming oxygen vacancies and water. It was also found that the presence of O2 during the H2 gas exposure caused the recombination of a number of oxygen vacancies and reduced the available surface catalytic sites for H2.