Oxidation mechanism of allyl alcohol on an Au-electrode in basic solutions

Celdrán, R.; González‐Velasco, J.

doi:10.1016/0013-4686(81)87033-8

Cited by 21 publications

(6 citation statements)

References 4 publications

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“…We now discuss the electrochemical data from previous work [16–20] for the atomic metal catalysts, and finally show that our DFT predicted hydroxyl radical binding energies exhibit excellent correlation with these measurements. Aliphatic alcohols can be electrochemically oxidized in alkaline medium [37,38] . This is a relatively complex electrochemical reaction that has been studied on bare solid electrodes, [38,39] on activated carbon electrode, [40] and also on Pt electrodes coated with a thin layer of polyaniline (PANI) [24,41] .…”

Section: Resultsmentioning

confidence: 99%

“…The relevant electrochemical reactions involved in the n‐propanol oxidation [37,38] are discussed in context of Figure 6. On the anodic sweep, there is a continuous generation (Eq.1) of the hydroxyl radical OH⋅ at the Pt by small but finite anodic current (Figure 6, point 1); it is postulated that the π system of the polyaniline matrix stabilizes the generated OH⋅ species [20] .…”

Section: Resultsmentioning

confidence: 99%

“…Aliphatic alcohols can be electrochemically oxidized in alkaline medium. [37,38] This is a relatively complex electrochemical reaction that has been studied on bare solid electrodes, [38,39] on activated carbon electrode, [40] and also on Pt electrodes coated with a thin layer of polyaniline (PANI). [24,41] We note that recent ab initio studies have elucidated alcohol oxidation mechanisms on model heterogeneous catalysts, [42][43][44] but it is unknown how mechanisms are altered for the Pd m Au n catalysts in presence of the PANI support.…”

Section: Electrochemical Testing Of Catalytic Activitymentioning

confidence: 99%

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Quantized Electrodes: Atomic Palladium and Gold in Polyaniline

2021

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Electrochemically deposited Pd m Au n metal clusters on a polyaniline-coated Pt electrode have been shown to exhibit an "ordering effect", in which the catalytic activity for n-propanol oxidation depends sensitively on the precise order that the metal atoms are deposited. For example, tri-atomic Pd 2 Au clusters exhibit different catalytic activity for electrodeposition order PdÀ PdÀ Au compared to PdÀ AuÀ Pd on the polyaniline (PANI)/Pt matrix. In this work, we utilize density functional theory (DFT) to elucidate the structure and energetics of triatomic Pd m Au n clusters attached to a model PANI support. We provide a rationale for the experimentally observed "ordering effect" in terms of specific covalent interactions between the metal atoms and PANI framework that alter the net stability of the metal catalyst. We find that hydroxyl radical binding energies computed for the model catalytic systems provide a good descriptor for the experimentally measured catalytic activity for n-propanol oxidation. In addition, the good correlation between experiment/theory serves as additional confirmation of our proposed catalytic structures and rationale of the previously unexplained "ordering effect". Our study highlights the important role of the PANI support in determining the activity of uniquely-defined, atomic metal catalysts.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Electrochemical Testing Of Catalytic Activitymentioning

confidence: 99%

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Quantized Electrodes: Atomic Palladium and Gold in Polyaniline

2021

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“…The role of • OH in PFOS degradation was further probed with free radical scavengers, allyl alcohol (AA), or tertiary butanol (t-buOH), included in the EO systems. The π-orbitals and allylic carbon in AA enable it to react with hydroxyl free radicals on the positively charged anode surface ( • OH ads ), 69,70 whereas t-buOH only reacts effectively with the dissolved radical ( • OH dis ). 55,71 As seen in Figure 5c, the k obs decreased with the increase of AA concentrations, with PFOS degradation nearly fully inhibited in the presence of 1000 mM AA.…”

Section: Environmental Science and Technologymentioning

confidence: 99%

Degradation of Perfluorooctanesulfonate by Reactive Electrochemical Membrane Composed of Magnéli Phase Titanium Suboxide

Shi

Wang

et al. 2019

Environ. Sci. Technol.

122

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This study investigated the degradation of perfluorooctanesulfonate (PFOS) in a reactive electrochemical membrane (REM) system in which a porous Magneĺi phase titanium suboxide ceramic membrane served simultaneously as the anode and the membrane. Near complete removal (98.30 ± 0.51%) of PFOS was achieved under a cross-flow filtration mode at the anodic potential of 3.15 V vs standard hydrogen electrode (SHE). PFOS removal efficiency during the REM operation is much greater than that of the batch operation mode under the same anodic potential. A systematic reaction rate analysis in combination with electrochemical characterizations quantitatively elucidated the enhancement of PFOS removal in REM operation in relation to the increased electroactive surface area and improved interphase mass transfer. PFOS appeared to undergo rapid mineralization to CO 2 and F − , with only trace levels of short-chain perfluorocarboxylic acids (PFCAs, C 4 −C 8 ) identified as intermediate products. Density functional theory (DFT) simulations and experiments involving free radical scavengers indicated that PFOS degradation was initiated by direct electron transfer (DET) on anode to yield PFOS free radicals (PFOS • ), which further react with hydroxyl radicals that were generated by water oxidation and adsorbed on the anode surface ( • OH ads ). The attack of • OH ads is essential to PFOS degradation, because, otherwise, PFOS • may react with water and revert to PFOS.

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“…The most significant contributions in this area were by Conway, Vesselyev as well as Johnson, although others also impacted on the understanding of the electrooxidation [23][24][25][26][27][28][29]. Conway and workers extensively investigated the oxidation of Au in acidic as well as alkaline media where they identified the role of anion adsorbed on single crystals [22,[30][31][32][33][34][35].…”

Section: Electrochemical Oxidation At the Gold Electrodementioning

confidence: 99%

Recent progress in electrochemical oxidation of saccharides at gold and copper electrodes in alkaline solutions

Torto

2009

Bioelectrochemistry

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Oxidation mechanism of allyl alcohol on an Au-electrode in basic solutions

Cited by 21 publications

References 4 publications

Quantized Electrodes: Atomic Palladium and Gold in Polyaniline

Quantized Electrodes: Atomic Palladium and Gold in Polyaniline

Degradation of Perfluorooctanesulfonate by Reactive Electrochemical Membrane Composed of Magnéli Phase Titanium Suboxide

Recent progress in electrochemical oxidation of saccharides at gold and copper electrodes in alkaline solutions

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