Premium
Guaiacol Hydrodeoxygenation Mechanism on Pt(111): Insights from Density Functional Theory and Linear Free Energy Relations
Author(s) -
Lee Kyungtae,
Gu Geun Ho,
Mullen Charles A.,
Boateng Akwasi A.,
Vlachos Dionisios G.
Publication year - 2015
Publication title -
chemsuschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.412
H-Index - 157
eISSN - 1864-564X
pISSN - 1864-5631
DOI - 10.1002/cssc.201402940
Subject(s) - hydrodeoxygenation , guaiacol , catechol , chemistry , density functional theory , dehydrogenation , functional group , phenol , adsorption , organic chemistry , computational chemistry , photochemistry , catalysis , selectivity , polymer
Density functional theory is used to study the adsorption of guaiacol and its initial hydrodeoxygenation (HDO) reactions on Pt(111). Previous Brønsted–Evans–Polanyi (BEP) correlations for small open‐chain molecules are inadequate in estimating the reaction barriers of phenolic compounds except for the side group (methoxy) carbon‐dehydrogenation. New BEP relations are established using a select group of phenolic compounds. These relations are applied to construct a potential‐energy surface of guaiacol‐HDO to catechol. Analysis shows that catechol is mainly produced via dehydrogenation of the methoxy functional group followed by the CH x ( x <3) removal of the functional group and hydrogenation of the ring carbon, in contrast to a hypothesis of a direct demethylation path. Dehydroxylation and demethoxylation are slow, implying that phenol is likely produced from catechol but not through its direct dehydroxylation followed by aromatic carbon‐ring hydrogenation.