Acid–base concerted mechanism in the dehydration of 1,4-butanediol over bixbyite rare earth oxide catalysts
書誌事項
- 公開日
- 2014-05
- 権利情報
-
- https://www.elsevier.com/tdm/userlicense/1.0/
- DOI
-
- 10.1016/j.cattod.2013.08.005
- 公開者
- Elsevier BV
この論文をさがす
説明
Abstract Catalytic activity of rare earth oxides (REOs) in the vapor-phase dehydration of 1,4-butanediol to produce 3-buten-1-ol varies with lattice parameters of REOs. In order to clarify the adsorption structure and the reaction mechanism, adsorption energy of 1,4-butanediol on bixbyite REO, such as Sc 2 O 3 , Y 2 O 3 , Dy 2 O 3 , Ho 2 O 3 , and Er 2 O 3 , {2 2 2} surface was calculated with density functional theory (DFT), and paired interacting orbitals (PIO) calculation of the adsorption state between 1,4-butanediol and Er 2 O 3 was executed. The DFT study elucidates that the catalytic activity is correlated with adsorption energy. The PIO study clarifies the interactions between the reactive atoms of 1,4-butanediol and Er 2 O 3 surface: tridentate interactions between a position-2 hydrogen atom of diol and an oxygen anion on Er 2 O 3 and between each OH group of diol and erbium cations on Er 2 O 3 , and an intramolecular repulsive interaction between the position-1 carbon atom and the oxygen atom of OH group are observed. These results suggest that the position-2 hydrogen atom is firstly abstracted by a basic oxygen anion and that the position-1 hydroxyl group is subsequently abstracted by an acidic erbium cation. Another OH group on position 4 plays an important role of anchoring the diol to the Er 2 O 3 surface. Therefore, it is proved that the dehydration of 1,4-butanediol over REOs proceeds via acid–base concerted mechanism.
収録刊行物
-
- Catalysis Today
-
Catalysis Today 226 124-133, 2014-05
Elsevier BV
