Increase in adsorptivity of sulfonate anions on Pt (111) surface with drying of ionomer

Kodama, Kensaku; Jinnouchi, Ryosuke; Suzuki, Tomomichi; Murata, Hajime; Hatanaka, Tatsuya; Morimoto, Yu

doi:10.1016/j.elecom.2013.09.005

Cited by 75 publications

(77 citation statements)

References 12 publications

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“…Experimentally, vibrational spectroscopy and NR techniques and theoretically, molecular dynamics (MD) simulations have contributed to the understanding of Nafion/substrate interactions and structure. A recent vibrational spectroscopy study showed that the sulfonic groups of Nafion coordinate with Pt . A more recent study has found evidence of ether groups in the Nafion side chain to interact with Pt surface as well .…”

Section: Discussionmentioning

confidence: 99%

Probing interfacial interactions of nafion ionomer: Thermal expansion of nafion thin films on substrates of different hydrophilicity/hydrophobicity

Zhang

Davies

Karan

2019

J Polym Sci B Polym Phys

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Interfacial interactions of Nafion ionomer with superhydrophilic (Pt, Au), hydrophilic (SiO2), and hydrophobic (graphene, octyltrichlorosilane [OTS]‐modified SiO2) is investigated, using in situ thermal ellipsometry, by quantification of substrate‐ and thickness‐dependent thermal properties of the ultrathin Nafion films of nominal thickness ranging 25–135 nm. For sub‐50 nm thin Nafion films, the thermal expansion coefficient of films decreased in the order of most hydrophobic to most hydrophilic substrate: OTS > graphene > SiO2 > Au > Pt, implying weaker interpolymer and polymer–substrate interactions for films on hydrophobic substrates. Expansion coefficient of films on SiO2, graphene, and OTS‐modified SiO2 decreased with thickness whereas that of films on Au and Pt substrates increased with thickness. Above ~100 nm of thickness, films on all substrates converged toward a common value representative of bulk Nafion. Thermal transition temperature was found to be higher for films on hydrophilic SiO2 than that for films on hydrophobic graphene and OTS‐modified SiO2 but was not discernible for films on Au and Pt substrates. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019, 57, 343–352

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Section: Discussionmentioning

confidence: 99%

Probing interfacial interactions of nafion ionomer: Thermal expansion of nafion thin films on substrates of different hydrophilicity/hydrophobicity

Zhang

Davies

Karan

2019

J Polym Sci B Polym Phys

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“…1,[3][4][5] For improving the ORR performance, using an ionomer with a functional group that is less adsorptive to Pt surface is, therefore, expected to be effective. Recent studies, however, showed that a perfluorinated sulfonic acid polymer (e.g.…”

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confidence: 99%

Catalyst Poisoning Property of Sulfonimide Acid Ionomer on Pt (111) Surface

Kodama

Shinohara

Hasegawa

et al. 2014

J. Electrochem. Soc.

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115

105

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The catalyst poisoning property of a novel ionomer, NBC4, which has two sulfonimide acid groups in its side chain ended with a perfluorobutane, instead of sulfonic acid groups as Nafion does, was theoretically and experimentally compared with that of Nafion. A density functional theory combined with a continuum electrolyte theory showed that the adsorption is weaker for sulfonimide anion than for sulfonate anion on Pt (111) surface. Electrochemical measurements using Pt (111) surfaced single crystal electrodes covered with the ionomer films showed the weaker anion adsorption and higher ORR activity by ca. 50% at 0.82 V vs the reversible hydrogen electrode for NBC4 than for Nafion.) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 131.215.225.9 Downloaded on 2015-06-21 to IP ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 131.215.225.9 Downloaded on 2015-06-21 to IP ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 131.215.225.9 Downloaded on 2015-06-21 to IP ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 131.215.225.9 Downloaded on 2015-06-21 to IP

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“…It was demonstrated that the strength of anion adsorption on the Pt surface in CF 3 SO 3 H is weaker than that in H 2 SO 4 ; the anion (sulfonic acid group) originating from the Nafion® ionomer interacts weakly with the Pt surface [16][17][18][19]. Thus, CF 3 SO 3 H is an ideal compound to examine the influence of the Pt-anion interactions on the interfacial behavior of Pt in the potential ranges of UPD H and oxide formation and reduction [20,21].…”

Section: Introductionmentioning

confidence: 99%

Thermodynamics of the Under-Potential Deposition of Hydrogen on Polycrystalline Platinum in Aqueous Trifluoromethanesulfonic Acid Solution

et al. 2014

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Understanding of the electrocatalytic behavior of the Pt/Nafion® ionomer interface is of great importance to fuel cell technology. Trifluoromethanesulfonic acid (CF 3 SO 3 H) is used as an electrolyte because it is the smallest fluorinated sulfonic acid and serves as a suitable molecular model mimicking the Nafion® ionomer. The under-potential deposition of H (UPD H) on polycrystalline Pt electrode in CF 3 SO 3 H is investigated using cyclic voltammetry in the 278-333 K temperature (T) range. The general electrochemical adsorption isotherm is used to determine the Gibbs energy (−13≤Δ ec−UPD )≤+20 J mol −1 K −1 ), and enthalpy (−8≤Δ ec − ads H°(-H UPD )≤−43 kJ mol −1 ) of electro-adsorption, and the Pt-H UPD surface bond energy (+225≤E Pt−H UPD ≤+261 kJ mol −1 ). The lateral interactions between the H UPD adatoms are repulsive; the energy of lateral interactions is T-dependent (ω(H UPD )= a − b T) and is in the +14≤ω(H UPD )≤+22 kJ mol −1 range. The values of Δ ec − ads G°(H UPD ), Δ ec − ads S°(H UPD ), Δ ec − ads H°(H UPD ), and E Pt−H UPD for UPD H in CF 3 SO 3 H are very similar to the analogous values obtained in aqueous H 2 SO 4 and HClO 4 solutions. The anion present in the electrolyte has a small impact on UPD H and influences the values of Δ ec− ads G°(H UPD ) only over a narrow H UPD coverage range. The anion nature has practically no impact on the values of Δ ec− ads S°(H UPD ), Δ ec−ads H°(H UPD ), or E Pt−H UPD .

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Increase in adsorptivity of sulfonate anions on Pt (111) surface with drying of ionomer

Cited by 75 publications

References 12 publications

Probing interfacial interactions of nafion ionomer: Thermal expansion of nafion thin films on substrates of different hydrophilicity/hydrophobicity

Probing interfacial interactions of nafion ionomer: Thermal expansion of nafion thin films on substrates of different hydrophilicity/hydrophobicity

Catalyst Poisoning Property of Sulfonimide Acid Ionomer on Pt (111) Surface

Thermodynamics of the Under-Potential Deposition of Hydrogen on Polycrystalline Platinum in Aqueous Trifluoromethanesulfonic Acid Solution

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