Operando Identification of Dual Active Sites in Ca2IrO4Nanocrystals with Yttrium Substitutions Boosting Acidic Oxygen Evolution Reaction

Yuying Liu; Liang Cai; Qianqian Ji; Chao Wang; Ziyi Liu; Liyang Lv; Bing Tang; Hengli Duan; Fengchun Hu; Huijuan Wang; Na Li; Zhihu Sun; Wensheng Yan

doi:10.1021/acsenergylett.2c01683

Operando Identification of Dual Active Sites in Ca₂IrO₄Nanocrystals with Yttrium Substitutions Boosting Acidic Oxygen Evolution Reaction

Yuying Liu, Liang Cai^*, Qianqian Ji, Chao Wang, Ziyi Liu, Liyang Lv, Bing Tang, Hengli Duan, Fengchun Hu, Huijuan Wang, Na Li^*, Zhihu Sun, Wensheng Yan^*

^*Corresponding author for this work

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

19 Scopus citations

Abstract

Non-noble metal substitutions of the iridium sites in iridium-based complex oxides while boosting acidic oxygen evolution reaction (OER) is a promising method for developing efficient electrocatalysts, but this remains a huge challenge. Herein, we report yttrium substitution of iridium in Ca₂IrO₄(Ca₂Y_xIr_1-xO₄) nanocrystals for the first time, which is demonstrated by detailed structural characterizations using X-ray absorption spectra, X-ray diffraction patterns, and elemental mapping images. The synthesized Ca₂Y_0.2Ir_0.8O₄catalyst requires a low overpotential of only 213 mV, achieving an acidic OER current density of 10 mA cm^-2, which represents an approximately 203.7-fold improvement in iridium mass activity and 204.4-fold improvement in turnover frequency in comparison to that of IrO₂at 1.5 V vs RHE, respectively. Systematic characterizations of electronic structures reveal the synergistic effects between high-valence iridium sites and increased lattice oxygen concentration induced by Y³⁺substitutions, which greatly enhance the intrinsic OER activity of Ca₂Y_0.2Ir_0.8O₄. Operando X-ray absorption spectra and Raman spectra reveal the iridium and yttrium dual active sites during acidic OER. Our results provide a method for designing dual active sites in iridium-based complex oxides for highly active acidic OER electrocatalysts.

Original language	English (US)
Pages (from-to)	3798-3806
Number of pages	9
Journal	ACS Energy Letters
Volume	7
Issue number	11
DOIs	https://doi.org/10.1021/acsenergylett.2c01683
State	Published - Nov 11 2022

Bibliographical note

Funding Information:
This work was financially supported by the National Key Research and Development Program of China (2021YFA1600800); National Natural Science Foundation of China (Grant Nos. 11975234, 11775225, U2032150, U1932211, 12075243, 12005227, and 12105286); the Users with Excellence Program of Hefei Science Center CAS (Nos. 2020HSC-UE002, 2020HSC-CIP013, 2021HSC-UE002, and 2021HSC-UE003),; the Major Science and Technology Project of Anhui Province (202103a05020025); the Key Program of Research and Development of Hefei Science Center, CAS (2021HSC-KPRD002); the Fundamental Research Funds for the Central Universities (WK 2310000103); and the Postdoctoral Science Foundation of China (Grant Nos. 2020M682041 and 2020TQ0316) and was partially carried out at the USTC Center for Micro and Nanoscale Research and Fabrication. The authors thank Beijing Synchrotron Radiation Facility (BSRF), Shanghai Synchrotron Radiation Facility (SSRF), and Beamlines MCD-A and MCD-B (Soochow Beamline for Energy Materials) at NSRL for the synchrotron beamtime.

Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.

ASJC Scopus subject areas

Chemistry (miscellaneous)
Renewable Energy, Sustainability and the Environment
Fuel Technology
Energy Engineering and Power Technology
Materials Chemistry

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Access to Document

10.1021/acsenergylett.2c01683

Cite this

@article{b850d6b3ccc0431cb6f7d01ec03d7072,

title = "Operando Identification of Dual Active Sites in Ca2IrO4Nanocrystals with Yttrium Substitutions Boosting Acidic Oxygen Evolution Reaction",

abstract = "Non-noble metal substitutions of the iridium sites in iridium-based complex oxides while boosting acidic oxygen evolution reaction (OER) is a promising method for developing efficient electrocatalysts, but this remains a huge challenge. Herein, we report yttrium substitution of iridium in Ca2IrO4(Ca2YxIr1-xO4) nanocrystals for the first time, which is demonstrated by detailed structural characterizations using X-ray absorption spectra, X-ray diffraction patterns, and elemental mapping images. The synthesized Ca2Y0.2Ir0.8O4catalyst requires a low overpotential of only 213 mV, achieving an acidic OER current density of 10 mA cm-2, which represents an approximately 203.7-fold improvement in iridium mass activity and 204.4-fold improvement in turnover frequency in comparison to that of IrO2at 1.5 V vs RHE, respectively. Systematic characterizations of electronic structures reveal the synergistic effects between high-valence iridium sites and increased lattice oxygen concentration induced by Y3+substitutions, which greatly enhance the intrinsic OER activity of Ca2Y0.2Ir0.8O4. Operando X-ray absorption spectra and Raman spectra reveal the iridium and yttrium dual active sites during acidic OER. Our results provide a method for designing dual active sites in iridium-based complex oxides for highly active acidic OER electrocatalysts.",

author = "Yuying Liu and Liang Cai and Qianqian Ji and Chao Wang and Ziyi Liu and Liyang Lv and Bing Tang and Hengli Duan and Fengchun Hu and Huijuan Wang and Na Li and Zhihu Sun and Wensheng Yan",

note = "Funding Information: This work was financially supported by the National Key Research and Development Program of China (2021YFA1600800); National Natural Science Foundation of China (Grant Nos. 11975234, 11775225, U2032150, U1932211, 12075243, 12005227, and 12105286); the Users with Excellence Program of Hefei Science Center CAS (Nos. 2020HSC-UE002, 2020HSC-CIP013, 2021HSC-UE002, and 2021HSC-UE003),; the Major Science and Technology Project of Anhui Province (202103a05020025); the Key Program of Research and Development of Hefei Science Center, CAS (2021HSC-KPRD002); the Fundamental Research Funds for the Central Universities (WK 2310000103); and the Postdoctoral Science Foundation of China (Grant Nos. 2020M682041 and 2020TQ0316) and was partially carried out at the USTC Center for Micro and Nanoscale Research and Fabrication. The authors thank Beijing Synchrotron Radiation Facility (BSRF), Shanghai Synchrotron Radiation Facility (SSRF), and Beamlines MCD-A and MCD-B (Soochow Beamline for Energy Materials) at NSRL for the synchrotron beamtime. Publisher Copyright: {\textcopyright} 2022 American Chemical Society. All rights reserved.",

year = "2022",

month = nov,

day = "11",

doi = "10.1021/acsenergylett.2c01683",

language = "English (US)",

volume = "7",

pages = "3798--3806",

journal = "ACS Energy Letters",

issn = "2380-8195",

publisher = "American Chemical Society",

number = "11",

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T1 - Operando Identification of Dual Active Sites in Ca2IrO4Nanocrystals with Yttrium Substitutions Boosting Acidic Oxygen Evolution Reaction

AU - Liu, Yuying

AU - Cai, Liang

AU - Ji, Qianqian

AU - Wang, Chao

AU - Liu, Ziyi

AU - Lv, Liyang

AU - Tang, Bing

AU - Duan, Hengli

AU - Hu, Fengchun

AU - Wang, Huijuan

AU - Li, Na

AU - Sun, Zhihu

AU - Yan, Wensheng

N1 - Funding Information: This work was financially supported by the National Key Research and Development Program of China (2021YFA1600800); National Natural Science Foundation of China (Grant Nos. 11975234, 11775225, U2032150, U1932211, 12075243, 12005227, and 12105286); the Users with Excellence Program of Hefei Science Center CAS (Nos. 2020HSC-UE002, 2020HSC-CIP013, 2021HSC-UE002, and 2021HSC-UE003),; the Major Science and Technology Project of Anhui Province (202103a05020025); the Key Program of Research and Development of Hefei Science Center, CAS (2021HSC-KPRD002); the Fundamental Research Funds for the Central Universities (WK 2310000103); and the Postdoctoral Science Foundation of China (Grant Nos. 2020M682041 and 2020TQ0316) and was partially carried out at the USTC Center for Micro and Nanoscale Research and Fabrication. The authors thank Beijing Synchrotron Radiation Facility (BSRF), Shanghai Synchrotron Radiation Facility (SSRF), and Beamlines MCD-A and MCD-B (Soochow Beamline for Energy Materials) at NSRL for the synchrotron beamtime. Publisher Copyright: © 2022 American Chemical Society. All rights reserved.

PY - 2022/11/11

Y1 - 2022/11/11

N2 - Non-noble metal substitutions of the iridium sites in iridium-based complex oxides while boosting acidic oxygen evolution reaction (OER) is a promising method for developing efficient electrocatalysts, but this remains a huge challenge. Herein, we report yttrium substitution of iridium in Ca2IrO4(Ca2YxIr1-xO4) nanocrystals for the first time, which is demonstrated by detailed structural characterizations using X-ray absorption spectra, X-ray diffraction patterns, and elemental mapping images. The synthesized Ca2Y0.2Ir0.8O4catalyst requires a low overpotential of only 213 mV, achieving an acidic OER current density of 10 mA cm-2, which represents an approximately 203.7-fold improvement in iridium mass activity and 204.4-fold improvement in turnover frequency in comparison to that of IrO2at 1.5 V vs RHE, respectively. Systematic characterizations of electronic structures reveal the synergistic effects between high-valence iridium sites and increased lattice oxygen concentration induced by Y3+substitutions, which greatly enhance the intrinsic OER activity of Ca2Y0.2Ir0.8O4. Operando X-ray absorption spectra and Raman spectra reveal the iridium and yttrium dual active sites during acidic OER. Our results provide a method for designing dual active sites in iridium-based complex oxides for highly active acidic OER electrocatalysts.

AB - Non-noble metal substitutions of the iridium sites in iridium-based complex oxides while boosting acidic oxygen evolution reaction (OER) is a promising method for developing efficient electrocatalysts, but this remains a huge challenge. Herein, we report yttrium substitution of iridium in Ca2IrO4(Ca2YxIr1-xO4) nanocrystals for the first time, which is demonstrated by detailed structural characterizations using X-ray absorption spectra, X-ray diffraction patterns, and elemental mapping images. The synthesized Ca2Y0.2Ir0.8O4catalyst requires a low overpotential of only 213 mV, achieving an acidic OER current density of 10 mA cm-2, which represents an approximately 203.7-fold improvement in iridium mass activity and 204.4-fold improvement in turnover frequency in comparison to that of IrO2at 1.5 V vs RHE, respectively. Systematic characterizations of electronic structures reveal the synergistic effects between high-valence iridium sites and increased lattice oxygen concentration induced by Y3+substitutions, which greatly enhance the intrinsic OER activity of Ca2Y0.2Ir0.8O4. Operando X-ray absorption spectra and Raman spectra reveal the iridium and yttrium dual active sites during acidic OER. Our results provide a method for designing dual active sites in iridium-based complex oxides for highly active acidic OER electrocatalysts.

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U2 - 10.1021/acsenergylett.2c01683

DO - 10.1021/acsenergylett.2c01683

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