Enhancing the stability of cobalt spinel oxide towards sustainable oxygen evolution in acid

Li, Ailong; Kong, Shuang; Guo, Chenxi; Ooka, Hideshi; Adachi, Kiyohiro; Hashizume, Daisuke; Jiang, Qike; Han, Hongxian; Xiao, Jianping; Nakamura, Ryuhei

doi:10.1038/s41929-021-00732-9

Cited by 343 publications

(310 citation statements)

References 52 publications

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“…[46] Recently, the stability of the spinel-type Co 3 O 4 was enhanced in acid media by the partial substitution of the octahedral Co sites by octahedral Mn sites. [47] The improvement in stability was assigned to a modulation of the metal-oxygen binding energies (E MnÀ O > E CoO ), which agrees with thermodynamic studies. [48] Furthermore, Sugawara et al [49] proposed a higher metal-metal coordination in layered, tunnel and spinel oxides as beneficial for activity and stability in CoMn oxides.…”

Section: Introductionsupporting

confidence: 78%

“…The role of Mn in layered Co oxide has been attributed to the modulation of the electronic properties, resulting in a more efficient charge‐transfer [46] . Recently, the stability of the spinel‐type Co 3 O 4 was enhanced in acid media by the partial substitution of the octahedral Co sites by octahedral Mn sites [47] . The improvement in stability was assigned to a modulation of the metal‐oxygen binding energies (E Mn−O >E CoO ), which agrees with thermodynamic studies [48] .…”

Section: Introductionmentioning

confidence: 99%

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Stabilization of a Mn−Co Oxide During Oxygen Evolution in Alkaline Media

et al. 2022

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Improving the stability of electrocatalysts for the oxygen evolution reaction (OER) through materials design has received less attention than improving their catalytic activity. We explored the effects of Mn addition to a cobalt oxide for stabilizing the catalyst by comparing single phase CoO x and (Co 0.7 Mn 0.3 )O x films electrodeposited in alkaline solution. The obtained disordered films were classified as layered oxides using X-ray absorption spectroscopy (XAS). The CoO x films showed a constant decrease in the catalytic activity during cycling, confirmed by oxygen detection, while that of (Co 0.7 Mn 0.3 )O x remained constant within error as measured by electrochemical metrics. These trends were rationalized based on XAS analysis of the metal oxidation states, which were Co 2.7 + and Mn 3.7 + in the bulk and similar near the surface of (Co 0.7 Mn 0.3 )O x , before and after cycling. Thus, Mn in (Co 0.7 Mn 0.3 )O x successfully stabilized the bulk catalyst material and its surface activity during OER cycling. The development of stabilization approaches is essential to extend the durability of OER catalysts.

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Section: Introductionsupporting

confidence: 78%

Section: Introductionmentioning

confidence: 99%

Stabilization of a Mn−Co Oxide During Oxygen Evolution in Alkaline Media

et al. 2022

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“…Indeed, cobalt oxides have shown promising OER electrocatalysis in acidic media, although highly limited by its redox potential-dependent instability, since CoO x may rapidly dissolve either at open circuit conditions or under high applied potentials 29 – 32 . Some interesting advances in long-term stability were achieved by doping or processing techniques 33 – 35 .…”

Section: Introductionmentioning

confidence: 99%

Sustainable oxygen evolution electrocatalysis in aqueous 1 M H2SO4 with earth abundant nanostructured Co3O4

Garcés‐Pineda

González‐Cobos

et al. 2022

Nat Commun

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Earth-abundant electrocatalysts for the oxygen evolution reaction (OER) able to work in acidic working conditions are elusive. While many first-row transition metal oxides are competitive in alkaline media, most of them just dissolve or become inactive at high proton concentrations where hydrogen evolution is preferred. Only noble-metal catalysts, such as IrO2, are fast and stable enough in acidic media. Herein, we report the excellent activity and long-term stability of Co3O4-based anodes in 1 M H2SO4 (pH 0.1) when processed in a partially hydrophobic carbon-based protecting matrix. These Co3O4@C composites reliably drive O2 evolution a 10 mA cm–2 current density for >40 h without appearance of performance fatigue, successfully passing benchmarking protocols without incorporating noble metals. Our strategy opens an alternative venue towards fast, energy efficient acid-media water oxidation electrodes.

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“…The mechanistic understanding of the electrocatalytic oxygen evolution reaction (OER) in water electrolysis has rapidly developed in recent years (1)(2)(3)(4)(5)(6). Previous studies proposed two major mechanisms including the traditional adsorbate evolution mechanism (AEM) and the recently proposed lattice oxygen oxidation mechanism (LOM).…”

Section: Introductionmentioning

confidence: 99%

Artificially steering electrocatalytic oxygen evolution reaction mechanism by regulating oxygen defect contents in perovskites

Lü

Zheng

et al. 2022

Sci. Adv.

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The regulation of mechanism on the electrocatalysis process with multiple reaction pathways is more efficient and essential than conventional material engineering for the enhancement of catalyst performance. Here, by using oxygen evolution reaction (OER) as a model, which has an adsorbate evolution mechanism (AEM) and a lattice oxygen oxidation mechanism (LOM), we demonstrate a general strategy for steering the two mechanisms on various La x Sr 1− x CoO 3−δ . By delicately controlling the oxygen defect contents, the dominant OER mechanism on La x Sr 1− x CoO 3−δ can be arbitrarily transformed between AEM-LOM-AEM accompanied by a volcano-type activity variation trend. Experimental and computational evidence explicitly reveal that the phenomenon is due to the fact that the increased oxygen defects alter the lattice oxygen activity with a volcano-type trend and preserve the Co 0 state for preferably OER. Therefore, we achieve the co-optimization between the activity and stability of catalysts by altering the mechanism rather than a specific design of catalysts.

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Enhancing the stability of cobalt spinel oxide towards sustainable oxygen evolution in acid

Cited by 343 publications

References 52 publications

Stabilization of a Mn−Co Oxide During Oxygen Evolution in Alkaline Media

Stabilization of a Mn−Co Oxide During Oxygen Evolution in Alkaline Media

Sustainable oxygen evolution electrocatalysis in aqueous 1 M H2SO4 with earth abundant nanostructured Co3O4

Artificially steering electrocatalytic oxygen evolution reaction mechanism by regulating oxygen defect contents in perovskites

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