The Effect of Fe Dopant Location in Co(Fe)OOHxNanoparticles for the Oxygen Evolution Reaction

Zhaozong Sun; Anthony Curto; Jonathan Rodríguez-Fernández; Zegao Wang; Ayush Parikh; Jakob Fester; Mingdong Dong; Aleksandra Vojvodic; Jeppe V. Lauritsen

doi:10.1021/acsnano.1c07219

The Effect of Fe Dopant Location in Co(Fe)OOH_xNanoparticles for the Oxygen Evolution Reaction

Zhaozong Sun, Anthony Curto, Jonathan Rodríguez-Fernández, Zegao Wang, Ayush Parikh, Jakob Fester, Mingdong Dong, Aleksandra Vojvodic^*, Jeppe V. Lauritsen^*

^*Corresponding author for this work

Interdisciplinary Nanoscience Center - INANO-Fysik, iNANO-huset

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaper › Journal article › Research › peer-review

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Abstract

The addition of iron (Fe) can in certain cases have a strong positive effect on the activity of cobalt and nickel oxide nanoparticles in the electrocatalytic oxygen evolution reaction (OER). The reported optimal Fe dopant concentrations are, however, inconsistent, and the origin of the increased activity due to Fe dopants in mixed oxides has not been identified so far. Here, we combine density functional theory calculations, scanning tunneling microscopy, and OER activity measurements on atomically defined Fe-doped Co oxyhydroxide nanoparticles supported on a gold surface to establish the link between the activity and the Fe distribution and concentration within the oxyhydroxide phase. We find that addition of Fe results in distinct effects depending on its location on edge or basal plane sites of the oxyhydroxide nanoparticles, resulting in a nonlinear OER activity as a function of Fe content. Fe atom substitution itself does not lead to intrinsically more active OER sites than the best Co sites. Instead, the sensitivity to Fe promoter content is explained by the strong preference for Fe to locate on the most active edge sites of oxyhydroxide nanoparticles, which for low Fe concentrations stabilizes the particles but in higher concentrations leads to a shell structure with less active Fe on all edge positions. The optimal Fe content thereby becomes dependent on nanoparticle size. Our findings demonstrate that synthesis strategies that adjust not only the Fe concentration in mixed oxides but also its distribution within a catalyst nanoparticle can lead to enhanced OER performance.

Original language	English
Journal	ACS Nano
Volume	15
Issue	11
Pages (from-to)	18226-18236
Number of pages	11
ISSN	1936-0851
DOIs	https://doi.org/10.1021/acsnano.1c07219
Publication status	Published - Nov 2021

Keywords

cobalt-iron oxide
cyclic voltammetry (CV)
density functional theory (DFT)
doping effect
oxygen evolution reaction
scanning tunneling microscopy (STM)
X-ray photoemission spectroscopy (XPS)

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10.1021/acsnano.1c07219

AM - The Effect of Fe Dopant Location in Co(Fe)OOHx Nanoparticles for the Oxygen Evolution ReactionAccepted manuscript, 1.53 MBLicence: Other

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@article{80cebbb7ce0d49c895fc8b876f3e4822,

title = "The Effect of Fe Dopant Location in Co(Fe)OOHxNanoparticles for the Oxygen Evolution Reaction",

abstract = "The addition of iron (Fe) can in certain cases have a strong positive effect on the activity of cobalt and nickel oxide nanoparticles in the electrocatalytic oxygen evolution reaction (OER). The reported optimal Fe dopant concentrations are, however, inconsistent, and the origin of the increased activity due to Fe dopants in mixed oxides has not been identified so far. Here, we combine density functional theory calculations, scanning tunneling microscopy, and OER activity measurements on atomically defined Fe-doped Co oxyhydroxide nanoparticles supported on a gold surface to establish the link between the activity and the Fe distribution and concentration within the oxyhydroxide phase. We find that addition of Fe results in distinct effects depending on its location on edge or basal plane sites of the oxyhydroxide nanoparticles, resulting in a nonlinear OER activity as a function of Fe content. Fe atom substitution itself does not lead to intrinsically more active OER sites than the best Co sites. Instead, the sensitivity to Fe promoter content is explained by the strong preference for Fe to locate on the most active edge sites of oxyhydroxide nanoparticles, which for low Fe concentrations stabilizes the particles but in higher concentrations leads to a shell structure with less active Fe on all edge positions. The optimal Fe content thereby becomes dependent on nanoparticle size. Our findings demonstrate that synthesis strategies that adjust not only the Fe concentration in mixed oxides but also its distribution within a catalyst nanoparticle can lead to enhanced OER performance. ",

keywords = "cobalt-iron oxide, cyclic voltammetry (CV), density functional theory (DFT), doping effect, oxygen evolution reaction, scanning tunneling microscopy (STM), X-ray photoemission spectroscopy (XPS)",

author = "Zhaozong Sun and Anthony Curto and Jonathan Rodr{\'i}guez-Fern{\'a}ndez and Zegao Wang and Ayush Parikh and Jakob Fester and Mingdong Dong and Aleksandra Vojvodic and Lauritsen, {Jeppe V.}",

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year = "2021",

month = nov,

doi = "10.1021/acsnano.1c07219",

language = "English",

volume = "15",

pages = "18226--18236",

journal = "ACS Nano",

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The Effect of Fe Dopant Location in Co(Fe)OOH_xNanoparticles for the Oxygen Evolution Reaction. / Sun, Zhaozong; Curto, Anthony; Rodríguez-Fernández, Jonathan et al.
In: ACS Nano, Vol. 15, No. 11, 11.2021, p. 18226-18236.

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaper › Journal article › Research › peer-review

TY - JOUR

T1 - The Effect of Fe Dopant Location in Co(Fe)OOHxNanoparticles for the Oxygen Evolution Reaction

AU - Sun, Zhaozong

AU - Curto, Anthony

AU - Rodríguez-Fernández, Jonathan

AU - Wang, Zegao

AU - Parikh, Ayush

AU - Fester, Jakob

AU - Dong, Mingdong

AU - Vojvodic, Aleksandra

AU - Lauritsen, Jeppe V.

N1 - Publisher Copyright: ©

PY - 2021/11

Y1 - 2021/11

N2 - The addition of iron (Fe) can in certain cases have a strong positive effect on the activity of cobalt and nickel oxide nanoparticles in the electrocatalytic oxygen evolution reaction (OER). The reported optimal Fe dopant concentrations are, however, inconsistent, and the origin of the increased activity due to Fe dopants in mixed oxides has not been identified so far. Here, we combine density functional theory calculations, scanning tunneling microscopy, and OER activity measurements on atomically defined Fe-doped Co oxyhydroxide nanoparticles supported on a gold surface to establish the link between the activity and the Fe distribution and concentration within the oxyhydroxide phase. We find that addition of Fe results in distinct effects depending on its location on edge or basal plane sites of the oxyhydroxide nanoparticles, resulting in a nonlinear OER activity as a function of Fe content. Fe atom substitution itself does not lead to intrinsically more active OER sites than the best Co sites. Instead, the sensitivity to Fe promoter content is explained by the strong preference for Fe to locate on the most active edge sites of oxyhydroxide nanoparticles, which for low Fe concentrations stabilizes the particles but in higher concentrations leads to a shell structure with less active Fe on all edge positions. The optimal Fe content thereby becomes dependent on nanoparticle size. Our findings demonstrate that synthesis strategies that adjust not only the Fe concentration in mixed oxides but also its distribution within a catalyst nanoparticle can lead to enhanced OER performance.

AB - The addition of iron (Fe) can in certain cases have a strong positive effect on the activity of cobalt and nickel oxide nanoparticles in the electrocatalytic oxygen evolution reaction (OER). The reported optimal Fe dopant concentrations are, however, inconsistent, and the origin of the increased activity due to Fe dopants in mixed oxides has not been identified so far. Here, we combine density functional theory calculations, scanning tunneling microscopy, and OER activity measurements on atomically defined Fe-doped Co oxyhydroxide nanoparticles supported on a gold surface to establish the link between the activity and the Fe distribution and concentration within the oxyhydroxide phase. We find that addition of Fe results in distinct effects depending on its location on edge or basal plane sites of the oxyhydroxide nanoparticles, resulting in a nonlinear OER activity as a function of Fe content. Fe atom substitution itself does not lead to intrinsically more active OER sites than the best Co sites. Instead, the sensitivity to Fe promoter content is explained by the strong preference for Fe to locate on the most active edge sites of oxyhydroxide nanoparticles, which for low Fe concentrations stabilizes the particles but in higher concentrations leads to a shell structure with less active Fe on all edge positions. The optimal Fe content thereby becomes dependent on nanoparticle size. Our findings demonstrate that synthesis strategies that adjust not only the Fe concentration in mixed oxides but also its distribution within a catalyst nanoparticle can lead to enhanced OER performance.

KW - cobalt-iron oxide

KW - cyclic voltammetry (CV)

KW - density functional theory (DFT)

KW - doping effect

KW - oxygen evolution reaction

KW - scanning tunneling microscopy (STM)

KW - X-ray photoemission spectroscopy (XPS)

UR - http://www.scopus.com/inward/record.url?scp=85119280344&partnerID=8YFLogxK

U2 - 10.1021/acsnano.1c07219

DO - 10.1021/acsnano.1c07219

M3 - Journal article

C2 - 34726375

AN - SCOPUS:85119280344

SN - 1936-0851

VL - 15

SP - 18226

EP - 18236

JO - ACS Nano

JF - ACS Nano

IS - 11

ER -

The Effect of Fe Dopant Location in Co(Fe)OOH_xNanoparticles for the Oxygen Evolution Reaction

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