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Resolving the chemical identity of H2SO4 derived anions on Pt(111) electrodes: they're sulfate

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Abstract

Understanding how electrolyte composition controls electrocatalytic reactions requires molecular-level insight into electrode/electrolyte interaction. Perhaps the most basic aspect of this interaction, the speciation of the interfacial ion, is often controversial for even relatively simple systems. For example, for Pt(111) in 0.5 M H2SO4 it has long been debated whether the adsorbed anion is SO42−, HSO4 or an H3O+⋯SO42− ion pair. Here we apply interface-specific vibrational sum frequency (VSF) spectroscopy and theory to this problem and perform an isotope exchange study: we collect VSF spectra of Pt(111) in H2SO4(H2O) and D2SO4(D2O) as a function of bias and show that at all potentials they are identical. This is the most direct spectroscopic evidence to date that SO42− is the dominant adsorbate, despite the fact that at 0.5 M H2SO4 bulk solution is dominated by HSO4. This approach is based on the unique selection rule of the VSF spectroscopy and thus offers a new way of accessing general electrode/electrolyte interaction in electrocatalysis.

Graphical abstract: Resolving the chemical identity of H2SO4 derived anions on Pt(111) electrodes: they're sulfate

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Publication details

The article was received on 16 Jun 2019, accepted on 15 Aug 2019 and first published on 15 Aug 2019


Article type: Paper
DOI: 10.1039/C9CP03397A
Phys. Chem. Chem. Phys., 2019, Advance Article
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    Resolving the chemical identity of H2SO4 derived anions on Pt(111) electrodes: they're sulfate

    I. Y. Zhang, G. Zwaschka, Z. Wang, M. Wolf, R. K. Campen and Y. Tong, Phys. Chem. Chem. Phys., 2019, Advance Article , DOI: 10.1039/C9CP03397A

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