Identification of the Active-Layer Structures for Acidic Oxygen Evolution from 9R-BaIrO3Electrocatalyst with Enhanced Iridium Mass Activity

Na Li; Liang Cai; Chao Wang; Yue Lin; Jinzhen Huang; Hongyuan Sheng; Haibin Pan; Wei Zhang; Qianqian Ji; Hengli Duan; Wei Hu; Wenhua Zhang; Fengchun Hu; Hao Tan; Zhihu Sun; Bo Song; Song Jin; Wensheng Yan; Liang Cai

doi:10.1021/jacs.1c04087

Identification of the Active-Layer Structures for Acidic Oxygen Evolution from 9R-BaIrO₃Electrocatalyst with Enhanced Iridium Mass Activity

Na Li, Liang Cai^*, Chao Wang, Yue Lin, Jinzhen Huang, Hongyuan Sheng, Haibin Pan, Wei Zhang, Qianqian Ji, Hengli Duan, Wei Hu, Wenhua Zhang, Fengchun Hu, Hao Tan, Zhihu Sun, Bo Song, Song Jin^*, Wensheng Yan^*, Liang Cai^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

97 Scopus citations

Abstract

Iridium-based perovskites show promising catalytic activity for oxygen evolution reaction (OER) in acid media, but the iridium mass activity remains low and the active-layer structures have not been identified. Here, we report highly active 1 nm IrOx particles anchored on 9R-BaIrO3 (IrOx/9R-BaIrO3) that are directly synthesized by solution calcination followed by strong acid treatment for the first time. The developed IrOx/9R-BaIrO3 catalyst delivers a high iridium mass activity (168 A gIr-1), about 16 times higher than that of the benchmark acidic OER electrocatalyst IrO2 (10 A gIr-1), and only requires a low overpotential of 230 mV to reach a catalytic current density of 10 mA cm-2geo. Careful scanning transmission electron microscopy, synchrotron radiation-based X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy analyses reveal that, during the electrocatalytic process, the initial 1 nm IrOx nanoparticles/9R-BaIrO3 evolve into amorphous Ir4+OxHy/IrO6 octahedrons and then to amorphous Ir5+Ox/IrO6 octahedrons on the surface. Such high relative content of amorphous Ir5+Ox species derived from trimers of face-sharing IrO6 octahedrons in 9R-BaIrO3 and the enhanced metallic conductivity of the Ir5+Ox/9R-BaIrO3 catalyst are responsible for the excellent acidic OER activity. Our results provide new insights into the surface active-layer structure evolution in perovskite electrocatalysts and demonstrate new approaches for engineering highly active acidic OER nanocatalysts.

Original language	English (US)
Pages (from-to)	18001-18009
Number of pages	9
Journal	Journal of the American Chemical Society
Volume	143
Issue number	43
DOIs	https://doi.org/10.1021/jacs.1c04087
State	Published - Nov 3 2021

Bibliographical note

Funding Information:
This work was financially supported by the National Natural Science Foundation of China (grant nos. 11975234, 11775225, 12075243, and 12005227), users with excellence program of Hefei Science Center CAS, (no. 2019HSC-UE002, 2020HSC-UE002, 2020HSC–CIP013). H.S. and S.J. thank the support of US NSF CHE-1955074. The authors would like to thank BSRF, SSRF, and NSRL for the synchrotron beamtime. This work was partially carried out at the USTC Center for Micro and Nanoscale Research and Fabrication.

Publisher Copyright:
© 2021 American Chemical Society.

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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10.1021/jacs.1c04087

Cite this

Li, N., Cai, L., Wang, C., Lin, Y., Huang, J., Sheng, H., Pan, H., Zhang, W., Ji, Q., Duan, H., Hu, W., Zhang, W., Hu, F., Tan, H., Sun, Z., Song, B., Jin, S., Yan, W., & Cai, L. (2021). Identification of the Active-Layer Structures for Acidic Oxygen Evolution from 9R-BaIrO₃Electrocatalyst with Enhanced Iridium Mass Activity. Journal of the American Chemical Society, 143(43), 18001-18009. https://doi.org/10.1021/jacs.1c04087

@article{a63b233c8a79471cbe4d48b8cc1c85b5,

title = "Identification of the Active-Layer Structures for Acidic Oxygen Evolution from 9R-BaIrO3Electrocatalyst with Enhanced Iridium Mass Activity",

abstract = "Iridium-based perovskites show promising catalytic activity for oxygen evolution reaction (OER) in acid media, but the iridium mass activity remains low and the active-layer structures have not been identified. Here, we report highly active 1 nm IrOx particles anchored on 9R-BaIrO3 (IrOx/9R-BaIrO3) that are directly synthesized by solution calcination followed by strong acid treatment for the first time. The developed IrOx/9R-BaIrO3 catalyst delivers a high iridium mass activity (168 A gIr-1), about 16 times higher than that of the benchmark acidic OER electrocatalyst IrO2 (10 A gIr-1), and only requires a low overpotential of 230 mV to reach a catalytic current density of 10 mA cm-2geo. Careful scanning transmission electron microscopy, synchrotron radiation-based X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy analyses reveal that, during the electrocatalytic process, the initial 1 nm IrOx nanoparticles/9R-BaIrO3 evolve into amorphous Ir4+OxHy/IrO6 octahedrons and then to amorphous Ir5+Ox/IrO6 octahedrons on the surface. Such high relative content of amorphous Ir5+Ox species derived from trimers of face-sharing IrO6 octahedrons in 9R-BaIrO3 and the enhanced metallic conductivity of the Ir5+Ox/9R-BaIrO3 catalyst are responsible for the excellent acidic OER activity. Our results provide new insights into the surface active-layer structure evolution in perovskite electrocatalysts and demonstrate new approaches for engineering highly active acidic OER nanocatalysts.",

author = "Na Li and Liang Cai and Chao Wang and Yue Lin and Jinzhen Huang and Hongyuan Sheng and Haibin Pan and Wei Zhang and Qianqian Ji and Hengli Duan and Wei Hu and Wenhua Zhang and Fengchun Hu and Hao Tan and Zhihu Sun and Bo Song and Song Jin and Wensheng Yan and Liang Cai",

note = "Funding Information: This work was financially supported by the National Natural Science Foundation of China (grant nos. 11975234, 11775225, 12075243, and 12005227), users with excellence program of Hefei Science Center CAS, (no. 2019HSC-UE002, 2020HSC-UE002, 2020HSC–CIP013). H.S. and S.J. thank the support of US NSF CHE-1955074. The authors would like to thank BSRF, SSRF, and NSRL for the synchrotron beamtime. This work was partially carried out at the USTC Center for Micro and Nanoscale Research and Fabrication. Publisher Copyright: {\textcopyright} 2021 American Chemical Society.",

year = "2021",

month = nov,

day = "3",

doi = "10.1021/jacs.1c04087",

language = "English (US)",

volume = "143",

pages = "18001--18009",

journal = "Journal of the American Chemical Society",

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Li, N, Cai, L, Wang, C, Lin, Y, Huang, J, Sheng, H, Pan, H, Zhang, W, Ji, Q, Duan, H, Hu, W, Zhang, W, Hu, F, Tan, H, Sun, Z, Song, B, Jin, S, Yan, W & Cai, L 2021, 'Identification of the Active-Layer Structures for Acidic Oxygen Evolution from 9R-BaIrO₃Electrocatalyst with Enhanced Iridium Mass Activity', Journal of the American Chemical Society, vol. 143, no. 43, pp. 18001-18009. https://doi.org/10.1021/jacs.1c04087

TY - JOUR

T1 - Identification of the Active-Layer Structures for Acidic Oxygen Evolution from 9R-BaIrO3Electrocatalyst with Enhanced Iridium Mass Activity

AU - Li, Na

AU - Cai, Liang

AU - Wang, Chao

AU - Lin, Yue

AU - Huang, Jinzhen

AU - Sheng, Hongyuan

AU - Pan, Haibin

AU - Zhang, Wei

AU - Ji, Qianqian

AU - Duan, Hengli

AU - Hu, Wei

AU - Zhang, Wenhua

AU - Hu, Fengchun

AU - Tan, Hao

AU - Sun, Zhihu

AU - Song, Bo

AU - Jin, Song

AU - Yan, Wensheng

AU - Cai, Liang

N1 - Funding Information: This work was financially supported by the National Natural Science Foundation of China (grant nos. 11975234, 11775225, 12075243, and 12005227), users with excellence program of Hefei Science Center CAS, (no. 2019HSC-UE002, 2020HSC-UE002, 2020HSC–CIP013). H.S. and S.J. thank the support of US NSF CHE-1955074. The authors would like to thank BSRF, SSRF, and NSRL for the synchrotron beamtime. This work was partially carried out at the USTC Center for Micro and Nanoscale Research and Fabrication. Publisher Copyright: © 2021 American Chemical Society.

PY - 2021/11/3

Y1 - 2021/11/3

N2 - Iridium-based perovskites show promising catalytic activity for oxygen evolution reaction (OER) in acid media, but the iridium mass activity remains low and the active-layer structures have not been identified. Here, we report highly active 1 nm IrOx particles anchored on 9R-BaIrO3 (IrOx/9R-BaIrO3) that are directly synthesized by solution calcination followed by strong acid treatment for the first time. The developed IrOx/9R-BaIrO3 catalyst delivers a high iridium mass activity (168 A gIr-1), about 16 times higher than that of the benchmark acidic OER electrocatalyst IrO2 (10 A gIr-1), and only requires a low overpotential of 230 mV to reach a catalytic current density of 10 mA cm-2geo. Careful scanning transmission electron microscopy, synchrotron radiation-based X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy analyses reveal that, during the electrocatalytic process, the initial 1 nm IrOx nanoparticles/9R-BaIrO3 evolve into amorphous Ir4+OxHy/IrO6 octahedrons and then to amorphous Ir5+Ox/IrO6 octahedrons on the surface. Such high relative content of amorphous Ir5+Ox species derived from trimers of face-sharing IrO6 octahedrons in 9R-BaIrO3 and the enhanced metallic conductivity of the Ir5+Ox/9R-BaIrO3 catalyst are responsible for the excellent acidic OER activity. Our results provide new insights into the surface active-layer structure evolution in perovskite electrocatalysts and demonstrate new approaches for engineering highly active acidic OER nanocatalysts.

AB - Iridium-based perovskites show promising catalytic activity for oxygen evolution reaction (OER) in acid media, but the iridium mass activity remains low and the active-layer structures have not been identified. Here, we report highly active 1 nm IrOx particles anchored on 9R-BaIrO3 (IrOx/9R-BaIrO3) that are directly synthesized by solution calcination followed by strong acid treatment for the first time. The developed IrOx/9R-BaIrO3 catalyst delivers a high iridium mass activity (168 A gIr-1), about 16 times higher than that of the benchmark acidic OER electrocatalyst IrO2 (10 A gIr-1), and only requires a low overpotential of 230 mV to reach a catalytic current density of 10 mA cm-2geo. Careful scanning transmission electron microscopy, synchrotron radiation-based X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy analyses reveal that, during the electrocatalytic process, the initial 1 nm IrOx nanoparticles/9R-BaIrO3 evolve into amorphous Ir4+OxHy/IrO6 octahedrons and then to amorphous Ir5+Ox/IrO6 octahedrons on the surface. Such high relative content of amorphous Ir5+Ox species derived from trimers of face-sharing IrO6 octahedrons in 9R-BaIrO3 and the enhanced metallic conductivity of the Ir5+Ox/9R-BaIrO3 catalyst are responsible for the excellent acidic OER activity. Our results provide new insights into the surface active-layer structure evolution in perovskite electrocatalysts and demonstrate new approaches for engineering highly active acidic OER nanocatalysts.

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U2 - 10.1021/jacs.1c04087

DO - 10.1021/jacs.1c04087

M3 - Article

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SN - 0002-7863

VL - 143

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JO - Journal of the American Chemical Society

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