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Crystallographic and Geometrical Dependence of Water Oxidation Activity in Co-Based Layered Hydroxides

[Image: see text] Cobalt-based layered hydroxides (LHs) stand out as one of the best families of electroactive materials for the alkaline oxygen evolution reaction (OER). However, fundamental aspects such as the influence of the crystalline structure and its connection with the geometry of the catal...

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Autores principales: Sanchis-Gual, Roger, Hunt, Diego, Jaramillo-Hernández, Camilo, Seijas-Da Silva, Alvaro, Mizrahi, Martín, Marini, Carlo, Oestreicher, Víctor, Abellán, Gonzalo
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10407849/
https://www.ncbi.nlm.nih.gov/pubmed/37560192
http://dx.doi.org/10.1021/acscatal.3c01432
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author Sanchis-Gual, Roger
Hunt, Diego
Jaramillo-Hernández, Camilo
Seijas-Da Silva, Alvaro
Mizrahi, Martín
Marini, Carlo
Oestreicher, Víctor
Abellán, Gonzalo
author_facet Sanchis-Gual, Roger
Hunt, Diego
Jaramillo-Hernández, Camilo
Seijas-Da Silva, Alvaro
Mizrahi, Martín
Marini, Carlo
Oestreicher, Víctor
Abellán, Gonzalo
author_sort Sanchis-Gual, Roger
collection PubMed
description [Image: see text] Cobalt-based layered hydroxides (LHs) stand out as one of the best families of electroactive materials for the alkaline oxygen evolution reaction (OER). However, fundamental aspects such as the influence of the crystalline structure and its connection with the geometry of the catalytic sites remain poorly understood. Thus, to address this topic, we have conducted a thorough experimental and in silico study on the most important divalent Co-based LHs (i.e., α-LH, β-LH, and LDH), which allows us to understand the role of the layered structure and coordination environment of divalent Co atoms on the OER performance. The α-LH, containing both octahedral and tetrahedral sites, behaves as the best OER catalyst in comparison to the other phases, pointing out the role of the chemical nature of the crystalline structure. Indeed, density functional theory (DFT) calculations confirm the experimental results, which can be explained in terms of the more favorable reconstruction into an active Co(III)-based oxyhydroxide-like phase (dehydrogenation process) as well as the significantly lower calculated overpotential across the OER mechanism for the α-LH structure (exhibiting lower Egap). Furthermore, ex situ X-ray diffraction and absorption spectroscopy reveal the permanent transformation of the α-LH phase into a highly reactive oxyhydroxide-like stable structure under ambient conditions. Hence, our findings highlight the key role of tetrahedral sites on the electronic properties of the LH structure as well as their inherent reactivity toward OER catalysis, paving the way for the rational design of more efficient and low-maintenance electrocatalysts.
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spelling pubmed-104078492023-08-09 Crystallographic and Geometrical Dependence of Water Oxidation Activity in Co-Based Layered Hydroxides Sanchis-Gual, Roger Hunt, Diego Jaramillo-Hernández, Camilo Seijas-Da Silva, Alvaro Mizrahi, Martín Marini, Carlo Oestreicher, Víctor Abellán, Gonzalo ACS Catal [Image: see text] Cobalt-based layered hydroxides (LHs) stand out as one of the best families of electroactive materials for the alkaline oxygen evolution reaction (OER). However, fundamental aspects such as the influence of the crystalline structure and its connection with the geometry of the catalytic sites remain poorly understood. Thus, to address this topic, we have conducted a thorough experimental and in silico study on the most important divalent Co-based LHs (i.e., α-LH, β-LH, and LDH), which allows us to understand the role of the layered structure and coordination environment of divalent Co atoms on the OER performance. The α-LH, containing both octahedral and tetrahedral sites, behaves as the best OER catalyst in comparison to the other phases, pointing out the role of the chemical nature of the crystalline structure. Indeed, density functional theory (DFT) calculations confirm the experimental results, which can be explained in terms of the more favorable reconstruction into an active Co(III)-based oxyhydroxide-like phase (dehydrogenation process) as well as the significantly lower calculated overpotential across the OER mechanism for the α-LH structure (exhibiting lower Egap). Furthermore, ex situ X-ray diffraction and absorption spectroscopy reveal the permanent transformation of the α-LH phase into a highly reactive oxyhydroxide-like stable structure under ambient conditions. Hence, our findings highlight the key role of tetrahedral sites on the electronic properties of the LH structure as well as their inherent reactivity toward OER catalysis, paving the way for the rational design of more efficient and low-maintenance electrocatalysts. American Chemical Society 2023-07-24 /pmc/articles/PMC10407849/ /pubmed/37560192 http://dx.doi.org/10.1021/acscatal.3c01432 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Sanchis-Gual, Roger
Hunt, Diego
Jaramillo-Hernández, Camilo
Seijas-Da Silva, Alvaro
Mizrahi, Martín
Marini, Carlo
Oestreicher, Víctor
Abellán, Gonzalo
Crystallographic and Geometrical Dependence of Water Oxidation Activity in Co-Based Layered Hydroxides
title Crystallographic and Geometrical Dependence of Water Oxidation Activity in Co-Based Layered Hydroxides
title_full Crystallographic and Geometrical Dependence of Water Oxidation Activity in Co-Based Layered Hydroxides
title_fullStr Crystallographic and Geometrical Dependence of Water Oxidation Activity in Co-Based Layered Hydroxides
title_full_unstemmed Crystallographic and Geometrical Dependence of Water Oxidation Activity in Co-Based Layered Hydroxides
title_short Crystallographic and Geometrical Dependence of Water Oxidation Activity in Co-Based Layered Hydroxides
title_sort crystallographic and geometrical dependence of water oxidation activity in co-based layered hydroxides
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10407849/
https://www.ncbi.nlm.nih.gov/pubmed/37560192
http://dx.doi.org/10.1021/acscatal.3c01432
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