Mechanism of ethanol electrooxidation on mesoporous Pt electrode in acidic medium studied by a novel electrochemical mass spectrometry set-up

Flórez-Montaño, Jonathan; Garcı́a, Gonzalo; Guillén-Villafuerte, O.; Rodrı́guez, José Luis; Planes, Gabriel A.; Pastor, E.

doi:10.1016/j.electacta.2016.05.070

Cited by 58 publications

(69 citation statements)

References 49 publications

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“…Different classic electrochemical methods, as cyclic voltammetry (CV) and chronoamperometry and other spectroelectrochemical methods, such as, in situ Fourier transform infrared (FTIR) or differential electrochemical mass spectrometry (DEMS), have been widely employed for the elucidation of different mechanistic steps and for clarifying the presence of possible intermediates and products during the EOR on Pt surfaces. By compilation of all these studies, we recently provided a global mechanism for the EOR on Pt surfaces in acidic media (Scheme ) …”

Section: Introductionmentioning

confidence: 99%

“…By compilation of all these studies, we recently provided a global mechanism for the EOR on Pt surfaces in acidic media (Scheme 1). [5] The full oxidation of ethanol to carbon dioxide has a thermodynamic potential of 0.08 V vs SHE. However, it involves several steps such as adsorption, CÀ C bond scission, dehydrogenation, electrooxidation of adsorbed intermediates (e. g. CO and CH 3 species) and formation of soluble species (e. g. acetaldehyde and acetic acid) that strongly modify the reaction rate as well as the conversion efficiency for CO 2 formation.…”

Section: Introductionmentioning

confidence: 99%

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Well‐Defined Platinum Surfaces for the Ethanol Oxidation Reaction

2019

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Direct ethanol fuel cells are a promising technology for clean energy production. The ethanol oxidation reaction (EOR) is surface sensitive and, hence, the study of single‐crystal electrodes provides fundamental knowledge of the different activity of the metal crystal planes. However, for practical applications, metal nanoparticles dispersed on a porous support are generally used to enhance the efficiency and to reduce the catalyst cost. Although some research has been devoted to the development of shape‐controlled nanoparticles, the finding of an efficient, cost‐effective, and easily scaled‐up catalytic system remains a challenge. Furthermore, the use of a suitable support with a well‐defined nanoarchitecture is essential for the control of the catalyst reactivity. In this Review, a general overview of the performance of single‐crystal electrodes and unsupported/supported shape‐controlled nanoparticles for the EOR is presented, paying special attention to Pt surfaces. Finally, the major challenges and directions for future research are also discussed to guide the design of efficient shape‐controlled catalysts for the EOR.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Well‐Defined Platinum Surfaces for the Ethanol Oxidation Reaction

2019

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“…8) and an adsorbed CH 3 COH species (eg. 9)[21,22]. CH 3 CH 2 OH → (Pt-O-CH 2 CH 3 or Pt-CH(CH 3 )OH) + H + + e -…”

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Pt and PtRu catalyst bilayers increase efficiencies for ethanol oxidation in proton exchange membrane electrolysis and fuel cells

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2017

Journal of Power Sources

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Polarization curves, product distributions, and reaction stoichiometries have been measured for the oxidation of ethanol at anodes consisting of Pt and PtRu bilayers and a homogeneous mixture of the two catalysts. These anode structures all show synergies between the two catalysts that can be attributed to the oxidation of acetaldehyde produced at the PtRu catalyst by the Pt catalyst. The use of a PtRu layer over a Pt layer produces the strongest effect, with higher currents than a Pt on PtRu bilayer, mixed layer, or either catalyst alone, except for Pt at high potentials. Reaction stoichiometries (average number of electrons transferred per ethanol molecule) were closer to the values for Pt alone for both of the bilayer configurations but much lower for PtRu and mixed anodes. Although Pt alone would provide the highest overall fuel cell efficiency at low power densities, the PtRu on Pt bilayer would provide higher power densities without a significant loss of efficiency. The origin of the synergy between the Pt and PtRu catalysts was elucidated by separation of the total current into the individual components for generation of carbon dioxide and the acetaldehyde and acetic acid byproducts.

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“…], which then dehydrogenates to produce acetaldehyde (Refs. ):

true Pt + CH_{3} CH_{2} OH \to Pt - CH_{3} CH_{2} OH

true Pt - CH_{3} CH_{2} OH \to Pt - CHOHCH_{3} + normalH^{+} + normale^{-}

true Pt - CHOHCH_{3} \to Pt - CHOCH_{3} + normalH^{+} + normale^{-}

true PtCHOCH_{3} \to Pt + HCOCH_{3}

…”

Section: Resultsmentioning

confidence: 99%

Ethanol Oxidation on Sn‐modified Pt Single‐Crystal Electrodes: New Mechanistic Insights from On‐line Electrochemical Mass Spectrometry

et al. 2016

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The modification of low‐index Pt single crystals with a submonolayer coverage of Sn enhances the electroactivity of the electrode for the ethanol oxidation process in perchloric acid solution. The optimum Sn coverage for ethanol oxidation depends on the Pt crystallography, found to be approximately 0.26, 0.48, and 0.58 for Pt(100), Pt(111), and Pt(110), respectively; the Sn/Pt(110) system being the surface that exhibits the highest activity. On‐line electrochemical mass spectrometry experiments show that both on Pt(111) and Pt(110), the presence of Sn enhances the oxidation of ethanol to acetaldehyde. The further oxidation of acetaldehyde is sensitive to the Pt surface structure: on Pt(110) there are sites able to break the C−C bond in acetaldehyde to form CO2, whereas on Pt(111) such sites are not available and acetaldehyde is oxidized further to acetic acid.

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Mechanism of ethanol electrooxidation on mesoporous Pt electrode in acidic medium studied by a novel electrochemical mass spectrometry set-up

Cited by 58 publications

References 49 publications

Well‐Defined Platinum Surfaces for the Ethanol Oxidation Reaction

Well‐Defined Platinum Surfaces for the Ethanol Oxidation Reaction

Pt and PtRu catalyst bilayers increase efficiencies for ethanol oxidation in proton exchange membrane electrolysis and fuel cells

Ethanol Oxidation on Sn‐modified Pt Single‐Crystal Electrodes: New Mechanistic Insights from On‐line Electrochemical Mass Spectrometry

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