pH Effects on Hydrogen Evolution and Oxidation over Pt(111): Insights from First-Principles
Abstract
A long-standing question in electrocatalysis is how the electrolyte pH affects the catalytic activity of proton–electron transfer reactions. A prime example for this is the hydrogen evolution/oxidation reaction (HER/HOR) over metal catalysts. While it has long been established that alkaline conditions result in a more sluggish reaction kinetics than in acidic conditions, the underlying reason for this trend remains contentious. Here, we apply density functional calculations to evaluate prevailing hypotheses for the origin of this effect: shifts in hydrogen binding, proton donor, and water reorganization energy. We present a microkinetic model, based on ab initio reaction energetics of all possible elementary steps. Our model shows a good agreement with experimental trends. We find that with increasing pH, the proton donor changes from hydronium to water. In conclusion, our model suggests that the intrinsically larger barriers for the splitting of water with respect to hydronium are the cause of HER kinetics being slower in alkaline than in acidic media.
- Authors:
-
[1];
[1];
[2]
- Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Technical Univ. of Denmark, Lyngby (Denmark)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
- OSTI Identifier:
- 1546960
- Grant/Contract Number:
- AC02-76SF00515
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Catalysis
- Additional Journal Information:
- Journal Volume: 9; Journal Issue: 7; Journal ID: ISSN 2155-5435
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; hydrogen evolution; electrocatalysis; DFT; microkinetic modeling; hydrogen oxidation; water splitting; kinetics
Citation Formats
Lamoureux, Philomena Schlexer, Singh, Aayush R., and Chan, Karen. pH Effects on Hydrogen Evolution and Oxidation over Pt(111): Insights from First-Principles. United States: N. p., 2019.
Web. doi:10.1021/acscatal.9b00268.
Lamoureux, Philomena Schlexer, Singh, Aayush R., & Chan, Karen. pH Effects on Hydrogen Evolution and Oxidation over Pt(111): Insights from First-Principles. United States. https://doi.org/10.1021/acscatal.9b00268
Lamoureux, Philomena Schlexer, Singh, Aayush R., and Chan, Karen. Wed .
"pH Effects on Hydrogen Evolution and Oxidation over Pt(111): Insights from First-Principles". United States. https://doi.org/10.1021/acscatal.9b00268. https://www.osti.gov/servlets/purl/1546960.
@article{osti_1546960,
title = {pH Effects on Hydrogen Evolution and Oxidation over Pt(111): Insights from First-Principles},
author = {Lamoureux, Philomena Schlexer and Singh, Aayush R. and Chan, Karen},
abstractNote = {A long-standing question in electrocatalysis is how the electrolyte pH affects the catalytic activity of proton–electron transfer reactions. A prime example for this is the hydrogen evolution/oxidation reaction (HER/HOR) over metal catalysts. While it has long been established that alkaline conditions result in a more sluggish reaction kinetics than in acidic conditions, the underlying reason for this trend remains contentious. Here, we apply density functional calculations to evaluate prevailing hypotheses for the origin of this effect: shifts in hydrogen binding, proton donor, and water reorganization energy. We present a microkinetic model, based on ab initio reaction energetics of all possible elementary steps. Our model shows a good agreement with experimental trends. We find that with increasing pH, the proton donor changes from hydronium to water. In conclusion, our model suggests that the intrinsically larger barriers for the splitting of water with respect to hydronium are the cause of HER kinetics being slower in alkaline than in acidic media.},
doi = {10.1021/acscatal.9b00268},
journal = {ACS Catalysis},
number = 7,
volume = 9,
place = {United States},
year = {Wed Jun 05 00:00:00 EDT 2019},
month = {Wed Jun 05 00:00:00 EDT 2019}
}
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