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Understanding the effect of H2O adsorption on reactant activation is of great importance in heterogeneous catalysis, which remains a grand challenge particularly in oxide catalyst systems with structural complexity. Herein, the effect of D2O adsorption on D2 activation over MgO nanocatalysts at different temperatures has been investigated by transmission Fourier transform infrared (FT-IR) and temperature-programmed desorption (TPD). Two sets of hydride and hydroxyl species produced from D2 dissociation at more active and less active Mg-O pairs can be observed by FT-IR, which all desorb via the product of D2 as confirmed by TPD experiments. We find that the physically adsorbed D2O overlayer does not affect the dissociation of D2 since D2 may pass through the molecular layer and access the surface-active sites. When D2O is partially dissociated on the MgO surface, D2 can only dissociate at the remaining active sites until that dissociated -ODw groups from D2O occupy all active sites. These findings provide a fundamental understanding of the effect of water adsorption on D2 activation on oxide catalysts.
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