Understanding the pH Dependence of Underpotential Deposited Hydrogen on Platinum

Yang, Xuan; Nash, Jared; Oliveira, Nicholas; Yan, Yushan; Xu, Bingjun

doi:10.1002/anie.201909697

Understanding the pH Dependence of Underpotential Deposited Hydrogen on Platinum

Journal Article · Wed Nov 06 00:00:00 EST 2019 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.201909697· OSTI ID:1803031

Yang, Xuan ^[1]; Nash, Jared ^[2]; Oliveira, Nicholas ^[2]; Yan, Yushan ^[2]; ^[2]

Univ. of Delaware, Newark, DE (United States). Center for Catalytic Science and Technology; OSTI
Univ. of Delaware, Newark, DE (United States). Center for Catalytic Science and Technology

Understanding the pH dependent shift of the oxidation peak of the underpotential deposited hydrogen (H_upd) in cyclic voltammograms on the Pt surface is of significance in terms of both the fundamentals of electrochemistry and the rational design of catalysts for the hydrogen oxidation/evolution reactions (HOR/HER). In this work, we provide compelling evidence that the pH dependent shift in the H_upd peak on Pt surfaces is driven by the structure of interfacial water rather than the specific adsorption of cations on the electrode surface. Additionally, combined cyclic voltammetric and surface enhanced spectroscopic investigations using an organic cation and crown-ether chelated alkali metal cations show that specific adsorption of metal and organic cations on the Pt surface at the conditions relevant to the HOR/HER is unlikely. The vibrational band corresponding to strongly bound water is monitored when the electrode potential is varied in the H_upd range in both acid and base.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Delaware, Newark, DE (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE; USDOE Office of Science (SC)

Grant/Contract Number:: SC0016537

OSTI ID:: 1803031

Alternate ID(s):: OSTI ID: 1573284

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 49 Vol. 58; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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interfacial water structure
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Understanding the pH Dependence of Underpotential Deposited Hydrogen on Platinum

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