Density functional theory study of lactic acid adsorption and dehydration reaction on monoclinic 011, (1)over-bar01, and (1)over-bar11 zirconia surfaces

作者：Hammaecher Catherine; Paul Jean Francois^*

来源：Journal of Catalysis, 2013, 300: 174-182.

DOI：10.1016/j.jcat.2012.11.030

• DFT
• Adsorption
• Monoclinic zirconia
• Lactic acid
• Dehydration reaction
• Carbocation
• Carbanion

Lactic acid adsorption and dehydration toward acrylic acid processes have been studied by means of density functional theory (DFT) calculations on 011, (1) over bar 01, and (1) over bar 11 monoclinic zirconia surfaces. Lactic acid presents two function types (carboxylic acid and alcohol). Therefore, seven modes of monodentate or bidentate adsorption have been characterized on the potential energy surfaces. Lactic acid is preferentially stabilized in a bidentate bridging mode with O-H bond dissociation whatever the studied surface. For the lactic acid dehydration reaction, two mechanisms have been studied. The carbocation formation by direct C-OH breaking proceeds with a very high activation energy ranging from 2.54 to 3.10 eV depending on the surface. On the contrary, lattice oxygen atoms can easily abstract a hydrogen atom from the methyl group of the lactic acid, and this reaction leads to carbanion formation with a lower activation energy ranging from 1.09 to 1.29 eV. Therefore, this mechanism could be a part of acrylic acid formation.

• 出版日期2013-4