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Nano Research 2023, 16(1): 334-342 https://doi.org/10.1007/s12274-022-4807-3
Research Article | Issue | Published: 02 September 2022

Sub-2 nm IrO2/Ir nanoclusters with compressive strain and metal vacancies boost water oxidation in acid

Show Author's Information Zhijuan Liu1,§,  Guangjin Wang3,§,  Jinyu Guo1,  Shuangyin Wang2( ),  Shuang-Quan Zang1( )
Henan Key Laboratory of Crystalline Molecular Functional Materials, Henan International Joint Laboratory of Tumor Theranostical Cluster Materials, Green Catalysis Center, and College of Chemistry, Zhengzhou University, Zhengzhou 450001, China
Hunan University, State Key Laboratory of Chem/Bio-sensing and Chemometrics, College of Chemistry and Chemical Engineering, Changsha 410082, China
School of Materials Science and Energy Engineering, Foshan University, Foshan 528000, China

§ Zhijuan Liu and Guangjin Wang contributed equally to this work.

Keywords:
compressive strain, d-band center, IrO2/Ir nanoclusters, metal vacancies, water oxidation in acid
Topics:
Oxygen evolution reaction
Cite this article:
Liu Z, Wang G, Guo J, et al. Sub-2 nm IrO2/Ir nanoclusters with compressive strain and metal vacancies boost water oxidation in acid. Nano Research, 2023, 16(1): 334-342. https://doi.org/10.1007/s12274-022-4807-3
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Abstract Full text Electronic supplementary material About this article

IrO2 exhibits good stability but limited electrocatalytic activity for oxygen evolution reaction in acid. Defect engineering is an effective strategy to improve the intrinsic ability of electrocatalysts by tailoring their electronic structure. Herein, we have successfully synthesized IrO2/Ir heterophase with compressive strain and metal vacancies via a simple substitution-etching method. In virtue of the solubility of Cr in strong alkali, metal vacancies could be formed at surface after etching Cr-doped IrO2/Ir in alkali, which leaded to modulated electronic structure. Meanwhile, the substitution of Cr with smaller atom radius would induce the formation of compressive strain and the relocated atoms made the d-band center shifted. With the regulated electronic structure and tuned d-band center, the obtained electrocatalyst only needed 285 mV to reach 10 mA·cm−2 in 0.1 M HClO4. Reaction kinetic has been rapidly accelerated as indicated by the smaller Tafel slope and charge transfer resistance. Theoretical calculations revealed that the d-band center and charge density distribution have been regulated with the introduction of defects in IrO2/Ir, which significantly decreased the free energy barrier of rate determining step. This work provides a valuable reference to design effective and defects-rich electrocatalysts.


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Electronic supplementary material
About this article

Sub-2 nm IrO2/Ir nanoclusters with compressive strain and metal vacancies boost water oxidation in acid

Show Author's information Zhijuan Liu1,§, Guangjin Wang3,§, Jinyu Guo1, Shuangyin Wang2( ), Shuang-Quan Zang1( )
Henan Key Laboratory of Crystalline Molecular Functional Materials, Henan International Joint Laboratory of Tumor Theranostical Cluster Materials, Green Catalysis Center, and College of Chemistry, Zhengzhou University, Zhengzhou 450001, China
Hunan University, State Key Laboratory of Chem/Bio-sensing and Chemometrics, College of Chemistry and Chemical Engineering, Changsha 410082, China
School of Materials Science and Energy Engineering, Foshan University, Foshan 528000, China

§ Zhijuan Liu and Guangjin Wang contributed equally to this work.

Abstract

IrO2 exhibits good stability but limited electrocatalytic activity for oxygen evolution reaction in acid. Defect engineering is an effective strategy to improve the intrinsic ability of electrocatalysts by tailoring their electronic structure. Herein, we have successfully synthesized IrO2/Ir heterophase with compressive strain and metal vacancies via a simple substitution-etching method. In virtue of the solubility of Cr in strong alkali, metal vacancies could be formed at surface after etching Cr-doped IrO2/Ir in alkali, which leaded to modulated electronic structure. Meanwhile, the substitution of Cr with smaller atom radius would induce the formation of compressive strain and the relocated atoms made the d-band center shifted. With the regulated electronic structure and tuned d-band center, the obtained electrocatalyst only needed 285 mV to reach 10 mA·cm−2 in 0.1 M HClO4. Reaction kinetic has been rapidly accelerated as indicated by the smaller Tafel slope and charge transfer resistance. Theoretical calculations revealed that the d-band center and charge density distribution have been regulated with the introduction of defects in IrO2/Ir, which significantly decreased the free energy barrier of rate determining step. This work provides a valuable reference to design effective and defects-rich electrocatalysts.

Keywords: compressive strain, d-band center, IrO2/Ir nanoclusters, metal vacancies, water oxidation in acid

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Publication history
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Acknowledgements

Publication history

Received: 26 April 2022
Revised: 20 July 2022
Accepted: 22 July 2022
Published: 02 September 2022
Issue date: January 2023

Copyright

© Tsinghua University Press 2022

Acknowledgements

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Nos. 92061201, 21825106, and 22102155), the China Postdoctoral Science Foundation (Nos. 2021M692909 and 2022T150587), the Program for Innovative Research Team (in Science and Technology) in Universities of Henan Province and Zhengzhou University (No. 19IRSTHN022), and the Key Scientific and Technological Project of Henan Province (No. 2021102210027).

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