부산대학교 도서관

The development of efficient heterogeneous catalysts for converting biomass into value-added chemical compounds remains at the forefront of catalysis research. Deoxydehydration (DODH) reaction that can transform vicinal hydroxy groups with the cis-configuration to the corresponding C═C bond in a single step is one of the promising techniques, and molybdenum oxide catalysts supported on TiO2have been reported as an effective catalyst using hydrogen as a reducing agent. Here, using density functional theory calculations, structures of monomeric and dimeric molybdenum oxide catalysts supported on anatase TiO2(101) have been determined, and we decipher the reaction mechanisms of the conversion of 1,4-anhydroerythritol to 2,5-dihydrofuran over these catalysts as a model reaction. We have found that MoO3and Mo2O5are the most stable structures for monomeric and dimeric species that exhibit the oxidation states of MoVIand MoV–MoVI, respectively, under the experimental conditions. For monomeric species, it is rather difficult to catalyze DODH reaction due to the instability for MoIVspecies and also the higher barrier for the C–O bond scission for MoVor MoVIspecies. For dimeric species, structures with the oxidation state of MoIV–MoVor MoV–MoVthat is found in the form of Mo2O4exhibit promising energy profiles in terms of stability and energy barrier (∼1.0 eV) for the C–O bond dissociation. Considering the experimental facts that MoIVspecies is responsible for the DODH reaction and Mo–Mo bond is present, the MoIV–MoVstructure could be the plausible active species. Our findings would provide useful information for the catalyst design using earth-abundant and less-expensive metal-based catalysts for the DODH reaction.