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Revealing the Active Intermediates in the Oxidation of Formic Acid on Au and Pt(111)

机译:揭示甲酸在Au和Pt上的氧化中的活性中间体(111)

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摘要

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.
机译:利用密度泛函理论研究了在气相和电化学条件下甲酸(HCOOH)在Au(111)上的氧化机理,并与Pt(111)上的类似过程进行了比较。我们的结果表明,涉及单个中间分子的机理在Au和Pt(111)上均是优选的。此外,在气相条件下,HCOOH氧化通过Au和Pt(111)上的相同机理(甲酸酯途径)进行,而在电化学条件下,HCOOH氧化可以通过明显不同的机理(甲酸酯和/或直接途径)进行在施加的电极电位上我们的计算有助于合理化矛盾的实验解释,对于理解这一基本(电)催化过程的机理至关重要。

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