Resolving Potential-Dependent Degradation of Electrodeposited Ni(OH)2 Catalysts in Alkaline Oxygen Evolution Reaction (OER): In Situ XANES Studies

[Display omitted] •In situ XANES analysis coupled with CV measurements identified the activation and two-stage degradation mechanisms of Ni-LDH catalysts in OER.•First and second stages of degradation are due to isolation of γ-NiOOH and overcharge of β-NiOOH.•Use of high-density carbon substrate for...

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Published in:Applied catalysis. B, Environmental Vol. 284; p. 119729
Main Authors: Lee, Sang-Yeon, Kim, Ik-Sun, Cho, Hyun-Seok, Kim, Chang-Hee, Lee, Yong-Kul
Format: Journal Article
Language:English
Published: Amsterdam Elsevier B.V 05-05-2021
Elsevier BV
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Summary:[Display omitted] •In situ XANES analysis coupled with CV measurements identified the activation and two-stage degradation mechanisms of Ni-LDH catalysts in OER.•First and second stages of degradation are due to isolation of γ-NiOOH and overcharge of β-NiOOH.•Use of high-density carbon substrate for Ni(OH)2 allowed a high and stable activity under potential changes. The activation and degradation mechanism of Ni-LDH catalysts electrodeposited on low and high-density carbon papers for the oxygen evolution reaction (OER) in alkaline media was investigated using in situ X-ray absorption near-edge structure (XANES) spectroscopy coupled with CV cycles in a potential range of 0–0.9 V (vs Hg/HgO), which allowed proposing two-stage degradation mechanisms with respect to cyclic voltammetry (CV) cycles. The electrodeposited α-Ni(OH)2 is firstly transformed to γ-NiOOH as an active phase in OER. In the reducible potential region, however, γ-NiOOH was partially reduced to β-Ni(OH)2, isolating the rest, which is the first stage of degradation. In the following anodic potential region, β-Ni(OH)2 is readily converted to β-NiOOH, which is mostly reversible, but only a small portion of β-NiOOH is overcharged to unstable γ-NiOOH, being responsible for the second stage degradation. It was noted that Ni(OH)2 catalysts electrodeposited on a low-density carbon paper (Ni-LC) underwent a severe degradation in the first stage, losing at least 56.9 % current density at 0.65 V (vs Hg/HgO), followed by a steady degradation in the second stage, while the use of a high-density carbon substrate (Ni−HC) effectively improved redox stability, maintaining a minimal loss of overpotential less than 5%, particularly with the second stage degradation being negligible even under potential changes, providing an important insight into designing durable and active Ni-LDH catalysts for the OER.
ISSN:0926-3373
1873-3883
DOI:10.1016/j.apcatb.2020.119729