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Title: 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:
ORCiD logo [1];  [2]; ORCiD logo [1]; ORCiD logo [1]
  1. California Inst. of Technology (CalTech), Pasadena, CA (United States)
  2. 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}
}

Journal Article:
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Cited by: 22 works
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Figures / Tables:

Figure 1 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 » white and Na in green.« less

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Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.