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Revealing the Active Intermediates in the Oxidation of Formic Acid on Au and Pt(111)
Author(s) -
Gao Wang,
Song Er Hong,
Jiang Qing,
Jacob Timo
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201402737
Subject(s) - formate , formic acid , electrochemistry , chemistry , catalysis , molecule , gas phase , density functional theory , mechanism (biology) , catalytic cycle , reaction mechanism , platinum , electrode , phase (matter) , inorganic chemistry , computational chemistry , photochemistry , organic chemistry , philosophy , epistemology
The mechanisms of formic acid (HCOOH) oxidation on Au(111) under gas‐phase and electrochemical conditions was studied by using density functional theory and then compared with the analogous processes on Pt(111). Our results demonstrate that a mechanism involving a single intermediate molecule is preferred on both Au and Pt(111). Furthermore, under gas‐phase conditions, HCOOH oxidation proceeds through the same mechanism (formate pathway) on Au and Pt(111), whereas under electrochemical conditions, it can take place through significantly different mechanisms (formate and/or direct pathways), depending on the applied electrode potential. Our calculations help to rationalize conflicting experimental explanations and are crucial for understanding the mechanism of this fundamental (electro‐)catalytic process.