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

Title: Understanding the pH Dependence of Underpotential Deposited Hydrogen on Platinum

Abstract

Abstract 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. 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.

Authors:

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

^[1]

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

Publication Date:: Wed Nov 06 00:00:00 EST 2019

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

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

OSTI Identifier:: 1803031

Alternate Identifier(s):: OSTI ID: 1573284

Grant/Contract Number:: SC0016537; CBET-1803200; CBET-1651625

Resource Type:: Accepted Manuscript

Journal Name:: Angewandte Chemie (International Edition)

Additional Journal Information:: Journal Name: Angewandte Chemie (International Edition); Journal Volume: 58; Journal Issue: 49; Journal ID: ISSN 1433-7851

Publisher:: Wiley

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; interfacial water structure; pH dependence; SEIRAS; specific adsorption; underpotential deposited hydrogen

Citation Formats


                    Yang, Xuan, Nash, Jared, Oliveira, Nicholas, Yan, Yushan, and Xu, Bingjun. Understanding the pH Dependence of Underpotential Deposited Hydrogen on Platinum.  United States: N. p., 2019. 
Web.  doi:10.1002/anie.201909697.

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                    Yang, Xuan, Nash, Jared, Oliveira, Nicholas, Yan, Yushan, & Xu, Bingjun. Understanding the pH Dependence of Underpotential Deposited Hydrogen on Platinum.  United States.  https://doi.org/10.1002/anie.201909697

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                    Yang, Xuan, Nash, Jared, Oliveira, Nicholas, Yan, Yushan, and Xu, Bingjun. Wed .  
"Understanding the pH Dependence of Underpotential Deposited Hydrogen on Platinum".  United States.  https://doi.org/10.1002/anie.201909697.  https://www.osti.gov/servlets/purl/1803031.

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@article{osti_1803031,

  title        = {Understanding the pH Dependence of Underpotential Deposited Hydrogen on Platinum},

  author       = {Yang, Xuan and Nash, Jared and Oliveira, Nicholas and Yan, Yushan and Xu, Bingjun},

  abstractNote = {Abstract 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. 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.},

  doi          = {10.1002/anie.201909697},

  journal      = {Angewandte Chemie (International Edition)},

  number       = 49,

  volume       = 58,

  place        = {United States},

  year         = {Wed Nov 06 00:00:00 EST 2019},

  month        = {Wed Nov 06 00:00:00 EST 2019}

}

Copy to clipboard

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Title: Understanding the pH Dependence of Underpotential Deposited Hydrogen on Platinum

Abstract

Citation Formats

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Determining the Viability of Hydroxide-Mediated Bifunctional HER/HOR Mechanisms through Single-Crystal Voltammetry and Microkinetic Modeling journal, January 2018

Water trapped in dibenzo-18-crown-6: Theoretical and spectroscopic (IR, Raman) studies journal, May 2006

Hydrogen Oxidation and Evolution Reaction Kinetics on Carbon Supported Pt, Ir, Rh, and Pd Electrocatalysts in Acidic Media journal, November 2014

Effect of Ions on the Structure of Water: Structure Making and Breaking journal, March 2009

Crystallization of Pb((Zn,Mg)1/3Nb2/3)O3-PbTiO3 Thin Films Via Immobilization of Pb2+ Ions During Sol-Gel Process: Crystallization of Pb((Zn,Mg)1/3Nb2/3)O3-PbTiO3 Thin Films
journal, August 2010

On the behavior of the Pt(100) and vicinal surfaces in alkaline media
journal, December 2011

Explanation of Dramatic pH-Dependence of Hydrogen Binding on Noble Metal Electrode: Greatly Weakened Water Adsorption at High pH
journal, May 2018

Surface-Enhanced Infrared Spectroscopy: The Origin of the Absorption Enhancement and Band Selection Rule in the Infrared Spectra of Molecules Adsorbed on Fine Metal Particles
journal, September 1993

Partial oxidation of step-bound water leads to anomalous pH effects on metal electrode step-edges
journal, January 2016

New insights into the electrochemical hydrogen oxidation and evolution reaction mechanism
journal, January 2014

Perspective—Towards Establishing Apparent Hydrogen Binding Energy as the Descriptor for Hydrogen Oxidation/Evolution Reactions
journal, January 2018

The role of non-covalent interactions in electrocatalytic fuel-cell reactions on platinum
journal, August 2009

Effect of Temperature on Hydrogen Adsorption on Pt(111), Pt(110), and Pt(100) Electrodes in 0.1 M HClO ₄
journal, January 2004

Electrochemical and infrared study of electro-oxidation of dimethyl ether (DME) on platinum polycrystalline electrode in acid solutions
journal, September 2008

Correlating Hydrogen Oxidation/Evolution Reaction Activity with the Minority Weak Hydrogen-Binding Sites on Ir/C Catalysts
journal, June 2015

Co-adsorption of Cations as the Cause of the Apparent pH Dependence of Hydrogen Adsorption on a Stepped Platinum Single-Crystal Electrode
journal, October 2017

Co-adsorption of Cations as the Cause of the Apparent pH Dependence of Hydrogen Adsorption on a Stepped Platinum Single-Crystal Electrode
journal, October 2017

Temperature dependent surface electrochemistry on Pt single crystals in alkaline electrolytes
journal, May 2002

A Conductance Study of 18-Crown-6 and Dibenzo-18-crown-6 Complexes with K ⁺ in Various Solvents
journal, March 1983

Vibrational Stark effect of adsorbates at electrochemical interfaces
journal, April 1996

Vibrational Properties of CO at the Pt(111)−Solution Interface: the Anomalous Stark-Tuning Slope
journal, January 2005

Universal dependence of hydrogen oxidation and evolution reaction activity of platinum-group metals on pH and hydrogen binding energy
journal, March 2016

Effect of the Interfacial Water Structure on the Hydrogen Evolution Reaction on Pt(111) Modified with Different Nickel Hydroxide Coverages in Alkaline Media
journal, December 2018

Adsorbed Hydroxide Does Not Participate in the Volmer Step of Alkaline Hydrogen Electrocatalysis
journal, November 2017

Ubiquitous Strategy for Probing ATR Surface-Enhanced Infrared Absorption at Platinum Group Metal−Electrolyte Interfaces
journal, April 2005

Hydrogen Oxidation and Evolution Reaction Kinetics on Platinum: Acid vs Alkaline Electrolytes
journal, January 2010

Infrared Reflection Absorption Spectroscopy of OH Adsorption on the Low Index Planes of Pt
journal, December 2014

Non-precious metal electrocatalysts with high activity for hydrogen oxidation reaction in alkaline electrolytes
journal, January 2014

Effect of Step Density and Orientation on the Apparent pH Dependence of Hydrogen and Hydroxide Adsorption on Stepped Platinum Surfaces
journal, July 2018

Impedance spectroscopy of H and OH adsorption on stepped single-crystal platinum electrodes in alkaline and acidic media
journal, January 2010

Temperature-Dependent Hydrogen Electrochemistry on Platinum Low-Index Single-Crystal Surfaces in Acid Solutions
journal, July 1997

Structure of Water at the Electrified Platinum−Water Interface: A Study by Surface-Enhanced Infrared Absorption Spectroscopy
journal, February 2008

Interfacial water reorganization as a pH-dependent descriptor of the hydrogen evolution rate on platinum electrodes
journal, March 2017

Effect of Monovalent Cations on the HOR/HER Activity for Pt in Alkaline Environment
journal, January 2019

The Comparability of Pt to Pt-Ru in Catalyzing the Hydrogen Oxidation Reaction for Alkaline Polymer Electrolyte Fuel Cells Operated at 80 °C
journal, January 2019

Poly(aryl piperidinium) membranes and ionomers for hydroxide exchange membrane fuel cells
journal, April 2019

The Central Role of Bicarbonate in the Electrochemical Reduction of Carbon Dioxide on Gold
journal, March 2017

Correlating hydrogen oxidation and evolution activity on platinum at different pH with measured hydrogen binding energy
journal, January 2015

pH and Alkali Cation Effects on the Pt Cyclic Voltammogram Explained Using Density Functional Theory
journal, December 2015

Structure and dynamics of hydrated ions
journal, May 1993

Towards the understanding of the interfacial pH scale at Pt(1 1 1) electrodes
journal, April 2015

Stark effect of adsorbate vibrations
journal, August 1984

Analysis of temperature effects on hydrogen and OH adsorption on Pt(111), Pt(100) and Pt(110) by means of Gibbs thermodynamics
journal, November 2010

Conductometric Studies on Cation-Crown Ether Complexes: A Review
journal, July 2011

Field-induced infrared absorption in metal surface spectroscopy: the electrochemical Stark effect
journal, May 1985

Recent advances in understanding the pH dependence of the hydrogen oxidation and evolution reactions
journal, November 2018

Cation-dependent restructure of the electric double layer on CO-covered Pt electrodes: Difference between hydrophilic and hydrophobic cations
journal, September 2017

Adsorption of water at Pt(111) electrode in HClO4 solutions. The potential of zero charge
journal, August 1996

Near-Infrared Spectral Studies for Investigating the Hydration of 18-Crown-6 in Aqueous Solutions
journal, March 1999

Surface enhanced spectroscopic investigations of adsorption of cations on electrochemical interfaces
journal, January 2017

Nickel supported on nitrogen-doped carbon nanotubes as hydrogen oxidation reaction catalyst in alkaline electrolyte
journal, January 2016

Determining the Viability of Hydroxide-Mediated Bifunctional HER/HOR Mechanisms through Single-Crystal Voltammetry and Microkinetic Modeling
journal, January 2018

Water trapped in dibenzo-18-crown-6: Theoretical and spectroscopic (IR, Raman) studies
journal, May 2006

Hydrogen Oxidation and Evolution Reaction Kinetics on Carbon Supported Pt, Ir, Rh, and Pd Electrocatalysts in Acidic Media
journal, November 2014

Effect of Ions on the Structure of Water: Structure Making and Breaking
journal, March 2009