Multiple adsorbate interactions between reduced CO2 adsorbates and either allyl alcohol or propargyl alcohol residues on platinum in 0.5 M sulphuric acid

Arévalo, M.C.; Gomis-Bas, C.; Pastor, E.; González, S.; Arvía, Alejandro Jorge

doi:10.1016/0013-4686(92)85226-b

Cited by 12 publications

(3 citation statements)

References 18 publications

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“…The oxidation of AA on Pt black yields acrolein as the principal reaction product [8]. Coadsorption phenomena and multiple adsorbate interactions between AA and CO2, CO and methanol have recently been reported [15,16]. The electro-oxidation of AA on Au [17,18] and Ru [19] in acids, has also been investigated.…”

Section: Introductionmentioning

confidence: 99%

DEMS and in-situ FTIR investigations of C3 primary alcohols on platinum electrodes in acid solutions.

Pastor

Wasmus

Iwasita

et al. 1993

Journal of Electroanalytical Chemistry

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Section: Introductionmentioning

confidence: 99%

DEMS and in-situ FTIR investigations of C3 primary alcohols on platinum electrodes in acid solutions.

Pastor

Wasmus

Iwasita

et al. 1993

Journal of Electroanalytical Chemistry

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“…The formation of r-CO 2 adsorbates from the CO:-containing solution on both Pt and Rh results from the interaction between the metal surface covered either partially or completely by H-adatoms, and CO 2 in the solution, although the presence of H-adatoms appears to be a necessary but not a sufficient condition for anchoring CO 2 on these metals [17]. However, the reactivity of CO 2 differs depending on whether strongly or weakly bound H-adatoms are involved [6,7], as can be deduced from the anodic stripping peak multiplicity for the corresponding adsorbates [7,18]. Therefore, although seemingly the behaviour of Rh and Pt for r-CO 2 adsorbate formation is qualitatively comparable, the potential for the highest yield of r-CO z adsorbates on Rh is more negative than that for Pt, and the electro-oxidation of r-CO 2 adsorbates on Rh is less clearly defined because of the overlapping of the early stages of O-electroadsorption which occurs at potentials below that for Pt.…”

Section: Possible Adsorbates Formed On Pt and Rh From Co: Dissolred In 05 M H2somentioning

confidence: 99%

Comparative electrochemical behaviour of CO2 on Pt and Rh electrodes in acid solution

Marcos

González‐Velasco

Bolzán

et al. 1995

Journal of Electroanalytical Chemistry

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The electroformation of adsorbed species on Pt and Rh from CO 2 dissolved in aqueous 0.5 M H2SO 4 and the influence of adsorbed species on the hydrogen evolution reaction (HER) were examined for smooth and columnar structured Pt and smooth and rhodized Rh electrodes at 25°C. Different electrosorbed species resulting from the adsorption of CO 2 on Rh were found. The electro-oxidation of these adsorbates on Rh takes place over a potential range larger than that for adsorbates on Pt, overlapping the potential range of electroformation of the O-containing layer. A part of the reduced CO 2 adsorbates on Rh behaves as CO-like adsorbates. The presence of adsorbed species from CO 2 influences differently the stationary HER current potential curves for both types of Pt and Rh electrodes. In the range of low current density (cd), the Tafel slope for Pt is -0.030 V decade 1. Conversely, the presence of a chemisorbed species on Rh changes the Tafel slope for the HER in the range of low cd from -0.030 V decade-~ for CO2-free solutions to -0.120 V decadefor CO2-saturated solution. These changes are explained by a modification in the rate-determining step of the HER produced by chemisorbed species.

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“…Studies of PA also include the interaction of adsorbed PA with CO, methanol, and CO 2 . , In particular, PA has attracted much attention in the context of mitigating global greenhouse gas emissions, offering the prospect of converting captured CO 2 into high-value chemicals by cyclization with PA. − Noble-metal free metal–organic frameworks have also demonstrated great potential for the cyclization of PA with CO 2 at atmospheric pressure and room temperature. , …”

Section: Introductionmentioning

confidence: 99%

Observation of Substituent Effects in the Electrochemical Adsorption and Hydrogenation of Alkynes on Pt{hkl} Using SHINERS

2020

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By combining cyclic voltammetry (CV) and shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS), the adsorption behavior of two alkynes, propargyl alcohol (PA) and 2-methyl-3-butyn-2-ol (MeByOH), undergoing hydrogenation on Pt basal plane single-crystal electrodes is investigated. It is found that PA and MeByOH give rise to strong surface sensitivities in relation to both hydrogenation activity and molecular fragmentation into adsorbed species such as CO. For PA, irreversible adsorption is strongly favored for Pt{100} and Pt{110} but is weak in the case of Pt{111}. It is suggested that the presence of the primary alcohol substituent is key to this behavior, with the order of surface reactivity being Pt{100} > Pt{110} > Pt{111}. In contrast, for MeByOH, strong irreversible adsorption is observed on all three basal plane Pt surfaces and we propose that this reflects the enhanced activity of the alkyne moiety arising from the inductive effect of the two methyl groups, coupled with the decreased activity of the tertiary alcohol substituent toward fragmentation. Pt{111} also exhibits singular behavior in relation to MeByOH hydrogenation in that a sharp Raman band at 1590 cm –1 is observed corresponding to the formation of a di-σ/π-bonded surface complex as the alkyne adsorbs. This band frequency is some 20 cm –1 higher than the analogous broadband observed for PA and MeByOH adsorbed on all other basal plane Pt surfaces and may be viewed as a fingerprint of Pt{111} terraces being present at a catalyst surface undergoing hydrogenation. Insights into the hydrogenation activity of different Pt{ hkl } surfaces are obtained using quantitative comparisons between Raman bands at hydrogenation potentials and at 0.4 V vs Pd/H, the beginning of the double-layer potential region, and it is asserted (with support from CV) that Pt{110} is the most active plane for hydrogenation due to the presence of surface defects generated via the lifting of the (1 × 2) to (1 × 1) clean surface reconstruction following flame annealing and hydrogen cooling. Our findings are also consistent with the hypothesis that Pt{111} planes are most likely to provide semihydrogenation selectivity of alkynes to alkenes, as reported previously.

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Multiple adsorbate interactions between reduced CO2 adsorbates and either allyl alcohol or propargyl alcohol residues on platinum in 0.5 M sulphuric acid

Cited by 12 publications

References 18 publications

DEMS and in-situ FTIR investigations of C3 primary alcohols on platinum electrodes in acid solutions.

DEMS and in-situ FTIR investigations of C3 primary alcohols on platinum electrodes in acid solutions.

Comparative electrochemical behaviour of CO2 on Pt and Rh electrodes in acid solution

Observation of Substituent Effects in the Electrochemical Adsorption and Hydrogenation of Alkynes on Pt{hkl} Using SHINERS

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