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Methanol Partial Oxidation on Ag(1 1 1) from First Principles
Author(s) -
Aljama Hassan,
Yoo Jong Suk,
Nørskov Jens K.,
AbildPedersen Frank,
Studt Felix
Publication year - 2016
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.201601053
Subject(s) - thermochemistry , partial oxidation , methanol , formaldehyde , chemistry , catalysis , dissociation (chemistry) , density functional theory , chemical kinetics , kinetics , reaction mechanism , oxygen , partial pressure , redox , bond cleavage , reaction intermediate , photochemistry , inorganic chemistry , computational chemistry , organic chemistry , physics , quantum mechanics
In this work, we examine the thermochemistry and kinetics of the partial oxidation of methanol to formaldehyde on silver surfaces. Periodic density functional theory calculations employing the BEEF‐vdW functional are used to identify the most stable phases of the silver surface under relevant reaction conditions and the reaction energetics are obtained on these surfaces. The calculated binding energies and transition state energies are used as input in a mean‐field microkinetic model providing the reaction kinetics on silver surfaces under different reaction conditions. Our results show that, under conditions pertaining to methanol partial oxidation, oxygen is present at low concentrations and it plays a critical role in the catalytic reaction. Surface oxygen promotes the reaction by activating the OH bond in methanol, thus forming a methoxy intermediate, which can react further to form formaldehyde. The dissociation of molecular oxygen is identified as the most critical step.