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Aqueous Phase Aldol Condensation of Formaldehyde and Acetone on Anatase TiO 2 (101) Surface: A Theoretical Investigation
Author(s) -
Zhao Yuntao,
Zhu Xinli,
Wang Hua,
Han Jinyu,
Mei Donghai,
Ge Qingfeng
Publication year - 2020
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201901736
Subject(s) - aldol condensation , anatase , dehydrogenation , chemistry , aqueous solution , density functional theory , condensation , catalysis , ab initio , aqueous two phase system , phase (matter) , acetone , chemical engineering , computational chemistry , photochemistry , organic chemistry , thermodynamics , physics , photocatalysis , engineering
A mechanistic understanding of catalytic reactions at solid‐liquid interface is limited both experimentally and theoretically but attracts much interest. Using density functional theory calculations (DFT) and ab initio molecular dynamics (AIMD) simulations, we investigated the effect of liquid water on α‐H abstraction, C−C coupling, and dehydration steps of aldol condensation of formaldehyde and acetone on an anatase TiO 2 (101) surface. The existence of the aqueous phase lowered the Gibbs energy of activation of dehydration step pronouncedly from 187 to 74 kJ/mol through proton transfer mechanism, making the hydrogenation pathway more favorable in the aqueous phase. In contrast, a mixed route prevails in the vapor phase. This work provides insights into the effect of the bulk water through a proton transfer mechanism on the dehydrogenation, C−C coupling, and dehydration steps.