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Title: Formic acid decomposition on polycrystalline platinum and palladized platinum electrodes

Abstract

This is a comprehensive study in which a formic acid decomposition reaction is examined as a probe of catalytic properties of polycrystalline platinum and palladized platinum electrodes. The electrode potential varies in a broad range, and the reaction is carried out in perchloric acid and sulfuric acid solutions containing different concentrations of HCOOH. Analytical methods used to access the decomposition reaction are chronoamperometry and cyclic voltammetry. At very short times, the authors prove that only a negligible amount of surface CO is formed, and the CO unaffected decomposition reaction, leading to CO{sub 2} formation, can be interrogated. Surprisingly, the decomposition reaction displays Tafel behavior only in a very narrow potential range. This observation, made with both clean Pt and Pt/Pd electrodes, suggests that water-surface interactions, and/or (bi)sulfate-surface interactions, increase with increasing electrode potential and create a steric/electronic barrier for the decomposition of formic acid (and methanol). The authors therefore offer a pessimistic view about platinum as a universal material for heterogeneous catalysis applications involving rearrangements of organic molecules. Such rearrangements may only be fulfilled with a low electrochemical driving force, at least at room temperature, but at higher potentials, the electrode becomes deactivated due to the unique attributes of themore » double layer structure on the platinum electrode. The authors have also found that the deceleration of formic acid oxidation (to CO{sub 2}) is primarily due to CO chemisorption only at potentials overlapping with those from the hydrogen adsorption range, or not too positive from this range. At more positive potentials, the decay in formic acid decomposition is neither due to CO formation nor to solution mass transfer limitations. The presence of interfacial CO{sub 2} or adsorption of formic acid and/or formate anion, could account for the decay. Finally, a detailed analysis of kinetic isotherms involved in the two pathways, CO{sub 2} formation and CO chemisorption, is made and the mechanism of formic acid decomposition on platinum is discussed. The electrolyte anion effects involved in formic acid oxidation in HClO{sub 4} and in H{sub 2}SO{sub 4} solutions are also presented.« less

Authors:
; ;
Publication Date:
Research Org.:
Univ. of Illinois, Urbana, IL (US)
Sponsoring Org.:
National Science Foundation (NSF); USDOE; US Department of the Army
OSTI Identifier:
20003204
DOE Contract Number:  
FG02-91ER45439
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical
Additional Journal Information:
Journal Volume: 103; Journal Issue: 44; Other Information: PBD: 4 Nov 1999
Country of Publication:
United States
Language:
English
Subject:
40 CHEMISTRY; FORMIC ACID; DECOMPOSITION; PLATINUM; PALLADIUM; CATALYTIC EFFECTS; ELECTRODES; CARBON MONOXIDE

Citation Formats

Lu, G Q, Crown, A, and Wieckowski, A. Formic acid decomposition on polycrystalline platinum and palladized platinum electrodes. United States: N. p., 1999. Web. doi:10.1021/jp992297x.
Lu, G Q, Crown, A, & Wieckowski, A. Formic acid decomposition on polycrystalline platinum and palladized platinum electrodes. United States. doi:10.1021/jp992297x.
Lu, G Q, Crown, A, and Wieckowski, A. Thu . "Formic acid decomposition on polycrystalline platinum and palladized platinum electrodes". United States. doi:10.1021/jp992297x.
@article{osti_20003204,
title = {Formic acid decomposition on polycrystalline platinum and palladized platinum electrodes},
author = {Lu, G Q and Crown, A and Wieckowski, A},
abstractNote = {This is a comprehensive study in which a formic acid decomposition reaction is examined as a probe of catalytic properties of polycrystalline platinum and palladized platinum electrodes. The electrode potential varies in a broad range, and the reaction is carried out in perchloric acid and sulfuric acid solutions containing different concentrations of HCOOH. Analytical methods used to access the decomposition reaction are chronoamperometry and cyclic voltammetry. At very short times, the authors prove that only a negligible amount of surface CO is formed, and the CO unaffected decomposition reaction, leading to CO{sub 2} formation, can be interrogated. Surprisingly, the decomposition reaction displays Tafel behavior only in a very narrow potential range. This observation, made with both clean Pt and Pt/Pd electrodes, suggests that water-surface interactions, and/or (bi)sulfate-surface interactions, increase with increasing electrode potential and create a steric/electronic barrier for the decomposition of formic acid (and methanol). The authors therefore offer a pessimistic view about platinum as a universal material for heterogeneous catalysis applications involving rearrangements of organic molecules. Such rearrangements may only be fulfilled with a low electrochemical driving force, at least at room temperature, but at higher potentials, the electrode becomes deactivated due to the unique attributes of the double layer structure on the platinum electrode. The authors have also found that the deceleration of formic acid oxidation (to CO{sub 2}) is primarily due to CO chemisorption only at potentials overlapping with those from the hydrogen adsorption range, or not too positive from this range. At more positive potentials, the decay in formic acid decomposition is neither due to CO formation nor to solution mass transfer limitations. The presence of interfacial CO{sub 2} or adsorption of formic acid and/or formate anion, could account for the decay. Finally, a detailed analysis of kinetic isotherms involved in the two pathways, CO{sub 2} formation and CO chemisorption, is made and the mechanism of formic acid decomposition on platinum is discussed. The electrolyte anion effects involved in formic acid oxidation in HClO{sub 4} and in H{sub 2}SO{sub 4} solutions are also presented.},
doi = {10.1021/jp992297x},
journal = {Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical},
number = 44,
volume = 103,
place = {United States},
year = {1999},
month = {11}
}