Explanation of Dramatic pH-Dependence of Hydrogen Binding on Noble Metal Electrode: Greatly Weakened Water Adsorption at High pH
Abstract
Hydrogen oxidation reaction (HOR) and hydrogen evolution reaction (HER) are both 2 orders slower in alkaline electrolyte than in acidic electrolyte, but no explanation has been provided. The first step toward understanding this dramatic pH-dependent HOR/HER performance is to explain the pH-dependent hydrogen binding to the electrode, a perplexing behavior observed experimentally. In this work, we carried out Quantum Mechanics Molecular Dynamics (QMMD) with explicit considerations of solvent and applied voltage (U) to in situ simulate water/Pt(100) interface in the condition of under-potential adsorption of hydrogen (HUPD). We found that as U is made more negative, the electrode tends to repel water, which in turn increases the hydrogen binding. We predicted a 0.13 eV increase in hydrogen binding from pH = 0.2 to pH = 12.8 with a slope of 10 meV/pH, which is close to the experimental observation of 8 to 12 meV/pH. Thus, we conclude that the changes in water adsorption are the major causes of pH-dependent hydrogen binding on a noble metal. Furthermore, the new insight of critical role of surface water in modifying electrochemical reactions provides a guideline in designing HER/HOR catalyst targeting for the alkaline electrolyte.
- Authors:
-
[1];
[1];
[1]
- California Inst. of Technology (CalTech), Pasadena, CA (United States)
- California Inst. of Technology (CalTech), Pasadena, CA (United States); Soochow Univ., Jiangsu (China)
- Publication Date:
- Research Org.:
- California Institute of Technology (CalTech), Pasadena, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1467598
- Grant/Contract Number:
- SC0004993
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 140; Journal Issue: 25; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Cheng, Tao, Wang, Lu, Merinov, Boris V., and Goddard, III, William A. Explanation of Dramatic pH-Dependence of Hydrogen Binding on Noble Metal Electrode: Greatly Weakened Water Adsorption at High pH. United States: N. p., 2018.
Web. doi:10.1021/jacs.8b04006.
Cheng, Tao, Wang, Lu, Merinov, Boris V., & Goddard, III, William A. Explanation of Dramatic pH-Dependence of Hydrogen Binding on Noble Metal Electrode: Greatly Weakened Water Adsorption at High pH. United States. https://doi.org/10.1021/jacs.8b04006
Cheng, Tao, Wang, Lu, Merinov, Boris V., and Goddard, III, William A. Thu .
"Explanation of Dramatic pH-Dependence of Hydrogen Binding on Noble Metal Electrode: Greatly Weakened Water Adsorption at High pH". United States. https://doi.org/10.1021/jacs.8b04006. https://www.osti.gov/servlets/purl/1467598.
@article{osti_1467598,
title = {Explanation of Dramatic pH-Dependence of Hydrogen Binding on Noble Metal Electrode: Greatly Weakened Water Adsorption at High pH},
author = {Cheng, Tao and Wang, Lu and Merinov, Boris V. and Goddard, III, William A.},
abstractNote = {Hydrogen oxidation reaction (HOR) and hydrogen evolution reaction (HER) are both 2 orders slower in alkaline electrolyte than in acidic electrolyte, but no explanation has been provided. The first step toward understanding this dramatic pH-dependent HOR/HER performance is to explain the pH-dependent hydrogen binding to the electrode, a perplexing behavior observed experimentally. In this work, we carried out Quantum Mechanics Molecular Dynamics (QMMD) with explicit considerations of solvent and applied voltage (U) to in situ simulate water/Pt(100) interface in the condition of under-potential adsorption of hydrogen (HUPD). We found that as U is made more negative, the electrode tends to repel water, which in turn increases the hydrogen binding. We predicted a 0.13 eV increase in hydrogen binding from pH = 0.2 to pH = 12.8 with a slope of 10 meV/pH, which is close to the experimental observation of 8 to 12 meV/pH. Thus, we conclude that the changes in water adsorption are the major causes of pH-dependent hydrogen binding on a noble metal. Furthermore, the new insight of critical role of surface water in modifying electrochemical reactions provides a guideline in designing HER/HOR catalyst targeting for the alkaline electrolyte.},
doi = {10.1021/jacs.8b04006},
journal = {Journal of the American Chemical Society},
number = 25,
volume = 140,
place = {United States},
year = {2018},
month = {5}
}
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Figure 1: The water/Pt (100) interface in QMMD simulations. (a) Explicit model (~6 water layers) (b) Explicit + Na+ model (~6 water layers + 1 Na) and (c) Explicit + Implicit model (~3 water layers + Implicit solvation model). The colors are Pt in silver, O in red, H inmore »
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Works referenced in this record:
Just a Dream—or Future Reality?
journal, April 2009
- Gasteiger, Hubert A.; Marković, Nenad M
- Science, Vol. 324, Issue 5923, p. 48-49
Electrocatalytic Oxygen Evolution Reaction (OER) on Ru, Ir, and Pt Catalysts: A Comparative Study of Nanoparticles and Bulk Materials
journal, July 2012
- Reier, Tobias; Oezaslan, Mehtap; Strasser, Peter
- ACS Catalysis, Vol. 2, Issue 8
New insights into the electrochemical hydrogen oxidation and evolution reaction mechanism
journal, January 2014
- Durst, J.; Siebel, A.; Simon, C.
- Energy Environ. Sci., Vol. 7, Issue 7
Electrocatalytic Measurement Methodology of Oxide Catalysts Using a Thin-Film Rotating Disk Electrode
journal, January 2010
- Suntivich, Jin; Gasteiger, Hubert A.; Yabuuchi, Naoaki
- Journal of The Electrochemical Society, Vol. 157, Issue 8
Benchmarking Heterogeneous Electrocatalysts for the Oxygen Evolution Reaction
journal, October 2013
- McCrory, Charles C. L.; Jung, Suho; Peters, Jonas C.
- Journal of the American Chemical Society, Vol. 135, Issue 45
A Perovskite Oxide Optimized for Oxygen Evolution Catalysis from Molecular Orbital Principles
journal, October 2011
- Suntivich, J.; May, K. J.; Gasteiger, H. A.
- Science, Vol. 334, Issue 6061
Design principles for hydrogen evolution reaction catalyst materials
journal, November 2016
- Strmcnik, Dusan; Lopes, Pietro Papa; Genorio, Bostjan
- Nano Energy, Vol. 29
Impedance spectroscopy of H and OH adsorption on stepped single-crystal platinum electrodes in alkaline and acidic media
journal, January 2010
- Schouten, K. J. P.; van der Niet, M. J. T. C.; Koper, M. T. M.
- Physical Chemistry Chemical Physics, Vol. 12, Issue 46
On the pH dependence of electrochemical proton transfer barriers
journal, March 2016
- Rossmeisl, Jan; Chan, Karen; Skúlason, Egill
- Catalysis Today, Vol. 262
Universal dependence of hydrogen oxidation and evolution reaction activity of platinum-group metals on pH and hydrogen binding energy
journal, March 2016
- Zheng, Jie; Sheng, Wenchao; Zhuang, Zhongbin
- Science Advances, Vol. 2, Issue 3
Hydrogen Oxidation and Evolution Reaction Kinetics on Carbon Supported Pt, Ir, Rh, and Pd Electrocatalysts in Acidic Media
journal, November 2014
- Durst, Julien; Simon, Christoph; Hasché, Frédéric
- Journal of The Electrochemical Society, Vol. 162, Issue 1
Correlating hydrogen oxidation and evolution activity on platinum at different pH with measured hydrogen binding energy
journal, January 2015
- Sheng, Wenchao; Zhuang, Zhongbin; Gao, Minrui
- Nature Communications, Vol. 6, Issue 1
Cyclic Voltammograms for H on Pt(111) and Pt(100) from First Principles
journal, September 2007
- Karlberg, G. S.; Jaramillo, T. F.; Skúlason, E.
- Physical Review Letters, Vol. 99, Issue 12
Perspective—Towards Establishing Apparent Hydrogen Binding Energy as the Descriptor for Hydrogen Oxidation/Evolution Reactions
journal, January 2018
- Zheng, Jie; Nash, Jared; Xu, Bingjun
- Journal of The Electrochemical Society, Vol. 165, Issue 2
Determination of the potentials of zero total charge of Pt(100) stepped surfaces in the [] zone. Effect of the step density and anion adsorption
journal, July 2003
- Domke, Katrin; Herrero, Enrique; Rodes, Antonio
- Journal of Electroanalytical Chemistry, Vol. 552
Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways
journal, February 2014
- Mathew, Kiran; Sundararaman, Ravishankar; Letchworth-Weaver, Kendra
- The Journal of Chemical Physics, Vol. 140, Issue 8
Chemisorption of Atomic Oxygen on Pt(111) from DFT Studies of Pt-Clusters
journal, September 2003
- Jacob, Timo; Muller, Richard P.; Goddard, William A.
- The Journal of Physical Chemistry B, Vol. 107, Issue 35
Covalent radii revisited
journal, January 2008
- Cordero, Beatriz; Gómez, Verónica; Platero-Prats, Ana E.
- Dalton Transactions, Issue 21
Partial oxidation of step-bound water leads to anomalous pH effects on metal electrode step-edges
journal, January 2016
- Schwarz, Kathleen; Xu, Bingjun; Yan, Yushan
- Physical Chemistry Chemical Physics, Vol. 18, Issue 24
pH and Alkali Cation Effects on the Pt Cyclic Voltammogram Explained Using Density Functional Theory
journal, December 2015
- McCrum, Ian T.; Janik, Michael J.
- The Journal of Physical Chemistry C, Vol. 120, Issue 1
Structure and Bonding of Water on Pt(111)
journal, December 2002
- Ogasawara, H.; Brena, B.; Nordlund, D.
- Physical Review Letters, Vol. 89, Issue 27
Two-Phase Thermodynamic Model for Efficient and Accurate Absolute Entropy of Water from Molecular Dynamics Simulations
journal, June 2010
- Lin, Shiang-Tai; Maiti, Prabal K.; Goddard, William A.
- The Journal of Physical Chemistry B, Vol. 114, Issue 24
On the absolute thermodynamics of water from computer simulations: A comparison of first-principles molecular dynamics, reactive and empirical force fields
journal, December 2012
- Pascal, Tod A.; Schärf, Daniel; Jung, Yousung
- The Journal of Chemical Physics, Vol. 137, Issue 24
Interfacial water reorganization as a pH-dependent descriptor of the hydrogen evolution rate on platinum electrodes
journal, March 2017
- Ledezma-Yanez, Isis; Wallace, W. David Z.; Sebastián-Pascual, Paula
- Nature Energy, Vol. 2, Issue 4
Works referencing / citing this record:
Hydrogen Evolution and Oxidation: Mechanistic Studies and Material Advances
journal, December 2018
- Tian, Xiaoyu; Zhao, Pengcheng; Sheng, Wenchao
- Advanced Materials, Vol. 31, Issue 31
CoP‐Doped MOF‐Based Electrocatalyst for pH‐Universal Hydrogen Evolution Reaction
journal, March 2019
- Liu, Teng; Li, Peng; Yao, Na
- Angewandte Chemie International Edition, Vol. 58, Issue 14
Theory-guided materials design: two-dimensional MXenes in electro- and photocatalysis
journal, January 2019
- Handoko, Albertus D.; Steinmann, Stephan N.; Seh, Zhi Wei
- Nanoscale Horizons, Vol. 4, Issue 4
Benchmarking the Activity, Stability, and Inherent Electrochemistry of Amorphous Molybdenum Sulfide for Hydrogen Production
journal, January 2019
- Escalera-López, Daniel; Lou, Zhiheng; Rees, Neil V.
- Advanced Energy Materials, Vol. 9, Issue 8
Understanding the pH Dependence of Underpotential Deposited Hydrogen on Platinum
journal, December 2019
- Yang, Xuan; Nash, Jared; Oliveira, Nicholas
- Angewandte Chemie International Edition, Vol. 58, Issue 49
Cable-like Ru/WNO@C nanowires for simultaneous high-efficiency hydrogen evolution and low-energy consumption chlor-alkali electrolysis
journal, January 2019
- Zhang, Lu-Nan; Lang, Zhong-Ling; Wang, Yong-Hui
- Energy & Environmental Science, Vol. 12, Issue 8
Understanding the pH Dependence of Underpotential Deposited Hydrogen on Platinum
journal, October 2019
- Yang, Xuan; Nash, Jared; Oliveira, Nicholas
- Angewandte Chemie, Vol. 131, Issue 49
Breaking the volcano-plot limits for Pt-based electrocatalysts by selective tuning adsorption of multiple intermediates
journal, January 2019
- Wang, Xuesi; He, Qun; Song, Li
- Journal of Materials Chemistry A, Vol. 7, Issue 22
Reaction intermediates during operando electrocatalysis identified from full solvent quantum mechanics molecular dynamics
journal, March 2019
- Cheng, Tao; Fortunelli, Alessandro; Goddard, William A.
- Proceedings of the National Academy of Sciences, Vol. 116, Issue 16
Anomalous hydrogen evolution behavior in high-pH environment induced by locally generated hydronium ions
journal, October 2019
- Wang, Xuesi; Xu, Chaochen; Jaroniec, Mietek
- Nature Communications, Vol. 10, Issue 1
CoP‐Doped MOF‐Based Electrocatalyst for pH‐Universal Hydrogen Evolution Reaction
journal, March 2019
- Liu, Teng; Li, Peng; Yao, Na
- Angewandte Chemie, Vol. 131, Issue 14
Ta 2 + -mediated ammonia synthesis from N 2 and H 2 at ambient temperature
journal, October 2018
- Geng, Caiyun; Li, Jilai; Weiske, Thomas
- Proceedings of the National Academy of Sciences, Vol. 115, Issue 46
General Construction of Molybdenum-Based Nanowire Arrays for pH-Universal Hydrogen Evolution Electrocatalysis
journal, September 2018
- Zhang, Xing; Zhou, Feng; Pan, Weiying
- Advanced Functional Materials, Vol. 28, Issue 43
Ruthenium Nanoparticles for Catalytic Water Splitting
journal, May 2019
- Creus, Jordi; De Tovar, Jonathan; Romero, Nuria
- ChemSusChem, Vol. 12, Issue 12
Towards membrane-electrode assembly systems for CO 2 reduction: a modeling study
journal, January 2019
- Weng, Lien-Chun; Bell, Alexis T.; Weber, Adam Z.
- Energy & Environmental Science, Vol. 12, Issue 6
Hierarchical nanoporous intermetallic compounds with self-grown transition-metal hydroxides as bifunctional catalysts for the alkaline hydrogen evolution reaction
journal, January 2019
- Han, Li-Ping; Yao, Rui-Qi; Wan, Wu-Bin
- Journal of Materials Chemistry A, Vol. 7, Issue 45
Synergistically Tuning Water and Hydrogen Binding Abilities Over Co 4 N by Cr Doping for Exceptional Alkaline Hydrogen Evolution Electrocatalysis
journal, September 2019
- Yao, Na; Li, Peng; Zhou, Zirui
- Advanced Energy Materials, Vol. 9, Issue 41
Energy–entropy competition in cation–hydroxyl interactions at the liquid water–Pt(111) interface
journal, January 2020
- Kristoffersen, Henrik H.; Chan, Karen; Vegge, Tejs
- Chemical Communications, Vol. 56, Issue 3
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