Title: Mechanistic understanding of pH effects on the oxygen evolution reaction

Journal Article · · Electrochimica Acta
 [1];  [1];  [2];  [3];  [3];  [4];  [3];  [5];  [5]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
  2. National Renewable Energy Lab. (NREL), Golden, CO (United States). Chemistry and Nanoscience Center
  3. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  4. Univ. of California, Berkeley, CA (United States)
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
+ Show Author Affiliations

The oxygen-evolution reaction (OER) is pivotal in many energy-conversion technologies as it is an important counter reaction to others that convert stable chemicals to higher-value products using electrochemistry. The local microenvironment and pH for the anode OER can vary from acidic to neutral to alkaline depending on the system being explored, making definitive mechanistic insights difficult. In this paper, we couple experiments, first-principles calculations based on density functional theory, microkinetics, and transport modeling to explore the entire pH range of the OER. At low current densities, neutral pH values unexpectedly perform better than the acidic and alkaline conditions, and this trend is reversed at higher current densities (> 20 mA cm-2). Using multiscale modeling, this switch is rationalized by a change from a dual-reaction mechanism to a single rate-determining step. The model also shows how the alkaline reaction rates dominate in the middle to high pH range. Furthermore, we explore that the local pH for near-neutral conditions is much different (e.g., 2.4 at the reaction surface vs. 9 in the bulk) than the pH extremes, demonstrating the criticality that transport phenomena plays in kinetic activity.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States); National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE National Nuclear Security Administration (NNSA); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Hydrogen and Fuel Cell Technologies Office; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Fuel Cell Technologies Office
Grant/Contract Number:
AC02-05CH11231; AC36-08GO28308; AC52-07NA27344
OSTI ID:
1841968
Report Number(s):
LLNL-JRNL-837583; NREL/JA-5900-81947; MainId:82720; UUID:9ad2b721-3bf2-4e77-adc1-a80eda0ddaad; MainAdminID:63698
Journal Information:
Electrochimica Acta, Journal Name: Electrochimica Acta Vol. 405; ISSN 0013-4686
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

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36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
electrochemistry
microkinetics
oxygen evolution
reaction