Electrosynthesis in aqueous medium: a kinetic study of the electrocatalytic oxidation of oxygenated organic molecules

Belgsir, E.M.; Bouhier, E.; Yei, H. Essis; Kokoh, K. Boniface; Beden, B.; Huser, Hervé; Léger, Jean‐Michel; Lamy, C.

doi:10.1016/0013-4686(91)85103-e

Cited by 95 publications

(58 citation statements)

References 17 publications

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“…Nevertheless, in the case of alcohol molecules (especially with various carbon atoms) intermediate aldehydes, ketones and acids play an important role. The limitation of the early HPLC studies was that the samples were taken from the electrolyte of the electrochemical cell [93,94] or from fuel cell anode output [95] which requires high concentration of these products for detection and the concentration of the products could be presented as a function of time. Since then these systems have been developed further and now HPLC can be combined with an electrochemical cell allowing the sample taken from the vicinity of the WE and the results can therefore be presented as a function of WE potential.…”

Section: Hplc Methodsmentioning

confidence: 99%

The correlation of electrochemical and fuel cell results for alcohol oxidation in acidic and alkaline media

Santasalo-Aarnio

Tuomi

Jalkanen

et al. 2013

Electrochimica Acta

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Section: Hplc Methodsmentioning

confidence: 99%

The correlation of electrochemical and fuel cell results for alcohol oxidation in acidic and alkaline media

Santasalo-Aarnio

Tuomi

Jalkanen

et al. 2013

Electrochimica Acta

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“…Adsorbed CO, C1 and C2 hydrocarbon residues have been identified as the major adsorbed intermediates on Pt-or Pd-based catalysts, while acetaldehyde and acetic acid have been detected as the main by-products using techniques such as infrared spectroscopy [13][14][15][16][17][18][19][20][21][22][23][24][25][26], online DEMS [27][28][29][30][31][32][33][34][35][36][37], ion chromatography [56,57], and liquid chromatography [14]. However, EOR has been shown to occur via a series of complex reactions involving a number of sequential and parallel reaction steps, thus resulting in more than 40 possible volatile and adsorbed intermediates or oxidative derivatives [43].…”

Section: Reaction Mechanism Of Eormentioning

confidence: 99%

Recent Advances on Electro-Oxidation of Ethanol on Pt- and Pd-Based Catalysts: From Reaction Mechanisms to Catalytic Materials

2015

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Abstract:The ethanol oxidation reaction (EOR) has drawn increasing interest in electrocatalysis and fuel cells by considering that ethanol as a biomass fuel has advantages of low toxicity, renewability, and a high theoretical energy density compared to methanol. Since EOR is a complex multiple-electron process involving various intermediates and products, the mechanistic investigation as well as the rational design of electrocatalysts are challenging yet essential for the desired complete oxidation to CO2. This mini review is aimed at presenting an overview of the advances in the study of reaction mechanisms and electrocatalytic materials for EOR over the past two decades with a focus on Pt-and Pd-based catalysts. We start with discussion on the mechanistic understanding of EOR on Pt and Pd surfaces using selected publications as examples. Consensuses from the mechanistic studies are that sufficient active surface sites to facilitate the cleavage of the C-C bond and the adsorption of water or its residue are critical for obtaining a higher electro-oxidation activity. We then show how this understanding has been applied to achieve improved performance on various Pt-and Pd-based catalysts through optimizing electronic and bifunctional effects, as well as by tuning their surface composition and structure. Finally we point out the remaining key problems in the development of anode electrocatalysts for EOR. OPEN ACCESSCatalysts 2015, 5 1508

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“…[18][19][20][21][22][23][24] The adsorbed CO and oxidation by-products block the Pt active sites, which results in a performance loss for both ORR and HOR.…”

Section: 4-9mentioning

confidence: 99%

mentioning

confidence: 99%

“…The electrochemical oxidation of EG on the Pt/C catalyst in acid media has attracted interest because of its potential application as a fuel for direct alcohol fuel cells. [17][18][19][20][21][22][23][24][25] In addition to the complete oxidation product CO 2 , the electro-oxidation of EG produces numerous stable, adsorbed species and partly oxidized by-products such as adsorbed CO, glycolic acid, oxalic acid, glycolaldehyde, glyoxal, glyoxylic acid, formaldehyde, and formic acid. [18][19][20][21][22][23][24] The adsorbed CO and oxidation by-products block the Pt active sites, which results in a performance loss for both ORR and HOR.…”

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confidence: 99%

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Effects of Ethylene Glycol and Caprolactam on the ORR and HOR Performances of Pt/C Catalysts

Zhai

St‐Pierre

2016

J. Electrochem. Soc.

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Ethylene glycol (EG) and caprolactam are two representative contaminant species either present in the fuel cell system or released by fuel cell system materials. The contamination effects of EG and caprolactam on the electro-catalytic performances of a Pt/C catalyst toward the oxygen reduction reaction (ORR) and hydrogen oxidation reaction (HOR) were investigated in acid media using the rotating ring/disk electrode (RRDE) technique. The Pt surface coverage increased with EG and caprolactam concentrations. The H 2 O 2 yield also significantly increased because of the effects of the two contaminants. The EG-and caprolactam-derived adsorbates reduce the ORR and HOR rates and modify the rate-determining step (change in Tafel Considering the inevitable depletion of conventional fossil fuels and the release of greenhouse gases into the Earth's atmosphere, it is necessary to look for renewable and clean energy supplies. Proton exchange membrane fuel cells (PEMFCs) are promising as clean energy sources for future automotive applications. However, the performance and durability of PEMFCs can be significantly decreased by the presence of contaminants in air and hydrogen or released by fuel cell system materials.1-3 Such species may adsorb on the Pt catalyst, penetrate into the ionomer and membrane, or compete with the main reactions, which decreases the active surface area, ionic conductivity of the catalyst layer and membrane, and cell performance. 2,4-9In addition, H 2 O 2 , which is a side product of the oxygen reduction reaction (ORR), and its associated yield often increases in the presence of organic contaminants such as acetylene, acetonitrile, propene, naphthalene, and methyl methacrylate. 10-13 A larger H 2 O 2 generation rate exerts an undetermined effect on the performance and durability of PEMFCs. The formation of H 2 O 2 has been linked to the radical attack decomposition of the Nafion ionomer, which is accelerated by the presence of Fe 2+ and Cu 2+ ions. 14,15 The Nafion ionomer is used as an electrolyte membrane and added to the catalyst layer to exploit its binding property and improve catalyst utilization. Consequently, the decomposition of the Nafion ionomer is a significant risk to the PEMFC performance and durability. Therefore, it is necessary to investigate the ORR, hydrogen oxidation reaction (HOR), and H 2 O 2 yield in the presence of contaminants to understand their effects on PEMFCs.This study was initiated with a list of system contaminants identified by the National Renewable Energy Laboratory (NREL).16 These were separated into 2 classes: linear and more structurally complex molecules including cyclic molecules (ring-shaped). One molecule of each class was chosen for these initial studies. Ethylene glycol (EG) is interesting because it is widely used as a coolant, antifreeze agent, and de-icing solution. De-icing of airport runways and airplanes is the primary source of EG in the environment. EG is also dispersed in the environment by the disposal of products that contain it. In addition, 1,6...

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Electrosynthesis in aqueous medium: a kinetic study of the electrocatalytic oxidation of oxygenated organic molecules

Cited by 95 publications

References 17 publications

The correlation of electrochemical and fuel cell results for alcohol oxidation in acidic and alkaline media

The correlation of electrochemical and fuel cell results for alcohol oxidation in acidic and alkaline media

Recent Advances on Electro-Oxidation of Ethanol on Pt- and Pd-Based Catalysts: From Reaction Mechanisms to Catalytic Materials

Effects of Ethylene Glycol and Caprolactam on the ORR and HOR Performances of Pt/C Catalysts

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