Reaction pathways of ethanol electrooxidation on polycrystalline platinum catalysts in acidic electrolytes

Kutz, Robert; Braunschweig, Björn; Mukherjee, Prabuddha; Behrens, Rachel L.; Dlott, Dana D.; Wiȩckowski, Andrzej

doi:10.1016/j.jcat.2010.11.018

Cited by 133 publications

(180 citation statements)

References 39 publications

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“…This interpretation is consistent with the results of Koper and co-workers [20], who evidenced the formation of ethylene (C 2 species) as a coproduct of carbon dioxide (C 1 species) reduction on copper electrodes. Other studies also support our interpretation about the high activity of the Pt toward breaking molecules into fragments and rearranging them [21,22]. In particular, a recent SFG study of 13 C-labeled ethanol electrooxidation on Pt shows cleavage of the C-C bond upon electrochemical adsorption [22].…”

Section: Resultssupporting

confidence: 80%

How Reactive are Metal Surfaces in Solution? A Comparison of the Electrochemical Adsorption of Organic Molecules on Pt At Low Potentials

2013

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Section: Resultssupporting

confidence: 80%

How Reactive are Metal Surfaces in Solution? A Comparison of the Electrochemical Adsorption of Organic Molecules on Pt At Low Potentials

2013

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“…According to the literature, 7 this shift is due the difference in the atomic radii of the metallic elements present in the alloy. For instance, Ru and Ni have smaller atomic radius (Ru = 134 pm, Ni =124 pm) as compared to Pt (138.5 pm).…”

Section: Resultsmentioning

confidence: 93%

“…[4][5][6] Ethanol is strongly adsorbed onto the platinum surface, which shifts the onset of oxidation potential to higher values, e.g., E > 0.8 V vs. RHE. In recent studies Kutz et al 7 using vibrational sum-frequency generation spectroscopy (SFG) found evidences that CO can be formed at lower potentials through fragments of CH x and CH x O oxidation indicating C−C bond breaking. Although the experimental conditions for cell operation is much different from the one employed in spectroscopic investigation one cannot discharge this findings.…”

Section: Introductionmentioning

confidence: 99%

Development of plurimetallic electrocatalysts prepared by decomposition of polymeric precursors for EtOH/O2 fuel cell

Palma¹,

Almeida²,

Andrade³

2012

J. Braz. Chem. Soc.

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Este trabalho teve como objetivo desenvolver eletrocatalisadores plurimetálicos contendo Pt, Ru, Ni e Sn suportados em C pelo método de decomposição de precursores poliméricos (DPP), na razão metal:carbono de 40:60% em massa, para aplicação em célula a combustível de etanol direta (DEFC). As nanopartículas obtidas foram caracterizadas físico-quimicamente por difração de raios X (DRX) e energia dispersiva de raios X. Os resultados de DRX revelaram cristalitos com estrutura cúbica de face centrada da Pt com evidências de que os átomos de Ni, Ru e Sn foram incorporados à estrutura da Pt. A caracterização eletroquímica das nanopartículas foi realizada por voltametria cíclica e cronoamperometria em meio ácido (H 2 SO 4 0,05 mol L -1 ), na ausência e presença de etanol. A adição de Sn para os catalisadores PtRuNi/C deslocou significativamente o potencial de início de oxidação de etanol e CO para valores mais baixos, aumentando assim a atividade catalítica, especialmente para a composição Pt 64 Sn 15 Ru 13 Ni 8 /C. Eletrólises de solução de etanol em 0,4 V vs. ERH permitiram a determinação de acetaldeído e ácido acético como principais produtos da reação. A presença de Ru nas ligas favoreceu a formação de ácido acético como produto principal da oxidação do etanol. O catalisador Pt 64 Sn 15 Ru 13 Ni 8 /C exibiu o melhor desempenho para DEFC.This work aimed to develop plurimetallic electrocatalysts composed of Pt, Ru, Ni, and Sn supported on C by decomposition of polymeric precursors (DPP), at a constant metal:carbon ratio of 40:60 wt.%, for application in direct ethanol fuel cell (DEFC). The obtained nanoparticles were physico-chemically characterized by X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy (EDX). XRD results revealed a face-centered cubic crystalline Pt with evidence that Ni, Ru, and Sn atoms were incorporated into the Pt structure. Electrochemical characterization of the nanoparticles was accomplished by cyclic voltammetry (CV) and chronoamperometry (CA) in slightly acidic medium (0.05 mol L -1 H 2 SO 4 ), in the absence and presence of ethanol. Addition of Sn to PtRuNi/C catalysts significantly shifted the ethanol and CO onset potentials toward lower values, thus increasing the catalytic activity, especially for the quaternary composition Pt 64 Sn 15 Ru 13 Ni 8 /C. Electrolysis of ethanol solutions at 0.4 V vs. RHE allowed determination of acetaldehyde and acetic acid as the main reaction products. The presence of Ru in alloys promoted formation of acetic acid as the main product of ethanol oxidation. The Pt 64 Sn 15 Ru 13 Ni 8 /C catalyst displayed the best performance for DEFC. Keywords: DEFC, ethanol, decomposition of polymeric precursor method (DPP), metallic catalyst IntroductionThe development of clean technologies for power generation with renewable fuels is required if we are to overcome the increase in environmental problems. In this context, the use of ethanol as fuel is promising because it is renewable, easy to store and handle, and contains high energy density (8 kW h kg -1 ),...

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“…The electrooxidation of organic compounds is not straightforward, as it proceeds as a branched, multistep, reaction [38,39]. Due to the large number of chemical bonds of the compounds, several reactions can be expected.…”

Section: Direct Alcohol Pem Fuel Cellsmentioning

confidence: 99%

“…Different reaction mechanisms have been proposed in the literature [38,44,45,50,106]. Due to the large amount of intermediate species, both free and adsorbed, and of potential elementary reactions, mathematical models exhibit different levels of complexity [77,107,108].…”

Section: The Ethanol Oxidation Reactionmentioning

confidence: 99%

Fundamentals of Electrochemistry with Application to Direct Alcohol Fuel Cell Modeling

Sánchez-Monreal¹,

Vera²,

García-Salaberri³

2018

Proton Exchange Membrane Fuel Cell

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Fuel cell modeling is an inherently multiphysics problem. As a result, scientists and engineers trained in different areas are required to work together in this field to address the complex physicochemical phenomena involved in the design and optimization of fuel cell systems. This multidisciplinary approach forces researchers to become accustomed to new concepts. Electrochemical processes, for example, constitute the heart of a fuel cell. Accurate modeling of electrochemical reactions is therefore essential to successfully predict the performance of these devices. However, becoming familiar with the complex concepts of electrochemistry can be an arduous task for those who approach the study of fuel cells from fields other than chemical engineering. This process can extend over time and requires careful reading of many textbooks and papers, the most illuminating ones being hidden to the newcomer in a plethora of recent publications on the subject. The authors, who engaged in the study of fuel cells coming from the field of mechanical engineering, had to travel this road once and, with this contribution, would like to make the journey easier for those who come behind. As an illustrative example, the thermodynamic and electrochemical principles reviewed in this chapter are applied to a complex electrochemical system, the direct ethanol fuel cell (DEFC), reviewing recent work on this problem and suggesting future research directions.

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Reaction pathways of ethanol electrooxidation on polycrystalline platinum catalysts in acidic electrolytes

Cited by 133 publications

References 39 publications

How Reactive are Metal Surfaces in Solution? A Comparison of the Electrochemical Adsorption of Organic Molecules on Pt At Low Potentials

How Reactive are Metal Surfaces in Solution? A Comparison of the Electrochemical Adsorption of Organic Molecules on Pt At Low Potentials

Development of plurimetallic electrocatalysts prepared by decomposition of polymeric precursors for EtOH/O2 fuel cell

Fundamentals of Electrochemistry with Application to Direct Alcohol Fuel Cell Modeling

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