Insights into the Electrochemical Oxidation and Reduction of Nickel Oxide Surfaces

Sun, Wenyu; Govindarajan, Nitish; Prajapati, Aditya; Huang, Jiayi; Bemana, Hossein; Feaster, Jeremy T.; Akhade, Sneha A.; Kornienko, Nikolay; Hahn, Christopher

doi:10.1021/acsami.4c13187

Title: Insights into the Electrochemical Oxidation and Reduction of Nickel Oxide Surfaces

Journal Article · 16 December 2024 · ACS Applied Materials and Interfaces

DOI: https://doi.org/10.1021/acsami.4c13187 · OSTI ID:2497911

^[1];

^[1]; Huang, Jiayi ^[2]; Bemana, Hossein ^[3]; Feaster, Jeremy T. ^[1];

^[1]; Kornienko, Nikolay ^[3];

^[1]

Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States). Laboratory for Energy Applications for the Future (LEAF)
Univ. of Montreal, QC (Canada)
Univ. of Montreal, QC (Canada); Univ. of Bonn (Germany)

Surface oxidation/reduction processes, driven by varying electrochemical potentials, can substantially impact catalyst effectiveness and, consequently, electrolyzer performance. Here, this study combines theoretical and experimental approaches to explore the surface redox behavior of nickel oxides, which are cost-effective and efficient catalysts for many electrochemical reactions. Surface Pourbaix diagrams for three different phases of nickel oxides, i.e., nickel hydroxide (Ni(OH)₂), nickel oxyhydroxide (NiOOH), and nickel dioxide (NiO₂), were constructed using density functional theory-based simulations. Various experimental methods, including cyclic voltammetry, in situ Raman spectroscopy, and electrochemical titration, were employed to probe the surface redox processes of nickel oxide thin films. Our findings indicate that the ABAB stacking sequence of Ni(OH)₂ lacks stability under oxidizing conditions to host the surface oxidation (deprotonation) events, while the AABBCC stacking sequence of NiOOH is energetically favorable due to the presence of interlayer hydrogen bonding. Rapid charge transfer facilitated by interlayer hydrogen bonding accounts for the higher reactivity of partially oxidized/reduced NiOOH (001) surfaces compared to Ni(OH)₂ (001) and NiO₂ (001) surfaces with the same stoichiometry, where interlayer hydrogen bonding is absent. Insights presented in this work can offer guidelines for optimizing operational conditions and tailoring the surface structures and oxidation states of nickel oxides to enhance performance in applications such as electrocatalysis and supercapacitors.

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Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 2497911

Report Number(s):: LLNL--JRNL-867084; 1102237

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 1 Vol. 17; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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36 MATERIALS SCIENCE
interlayer hydrogen bonding
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surface pourbaix diagram

Title: Insights into the Electrochemical Oxidation and Reduction of Nickel Oxide Surfaces

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