中国物理B ›› 2025, Vol. 34 ›› Issue (5): 57101-057101.doi: 10.1088/1674-1056/adc7f8

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Enhancing p-d hybridization via synergistic regulation of spatial and energetic orbital overlaps in Ba-doped LaNiO3 epitaxial films for oxygen evolution activity

Yingjia Li(李莹嘉), Xiang Xu(徐翔), Xiaoyu Qiu(邱晓宇), Jie Tu(涂杰), Zijian Chen(陈子健), Yujie Zhou(周雨洁), Zhao Guan(关赵), Youyuan Zhang(张友圆), Wen-Yi Tong(童文旖)†, Shaohui Xu(徐少辉), Ni Zhong(钟妮), Pinghua Xiang(向平华), Chun-Gang Duan(段纯刚), and Binbin Chen(陈斌斌)‡   

  1. Key Laboratory of Polar Materials and Devices (MOE) and Department of Electronics, East China Normal University, Shanghai 200241, China
  • 收稿日期:2025-02-27 修回日期:2025-03-25 接受日期:2025-04-02 出版日期:2025-04-18 发布日期:2025-05-06
  • 通讯作者: Wen-Yi Tong, Binbin Chen E-mail:wytong@ee.ecnu.edu.cn;bbchen@phy.ecnu.edu.cn
  • 基金资助:
    Project supported by the National Key R&D Program of China (Grant No. 2022YFA1402902), the National Natural Science Foundation of China (Grant Nos. 12374179, 12074119, 12374145, 051B22001, 12104157, 12134003, and 12304218), and the Shanghai Pujiang Program (Grant No. 23PJ1402200).

Enhancing p-d hybridization via synergistic regulation of spatial and energetic orbital overlaps in Ba-doped LaNiO3 epitaxial films for oxygen evolution activity

Yingjia Li(李莹嘉), Xiang Xu(徐翔), Xiaoyu Qiu(邱晓宇), Jie Tu(涂杰), Zijian Chen(陈子健), Yujie Zhou(周雨洁), Zhao Guan(关赵), Youyuan Zhang(张友圆), Wen-Yi Tong(童文旖)†, Shaohui Xu(徐少辉), Ni Zhong(钟妮), Pinghua Xiang(向平华), Chun-Gang Duan(段纯刚), and Binbin Chen(陈斌斌)‡   

  1. Key Laboratory of Polar Materials and Devices (MOE) and Department of Electronics, East China Normal University, Shanghai 200241, China
  • Received:2025-02-27 Revised:2025-03-25 Accepted:2025-04-02 Online:2025-04-18 Published:2025-05-06
  • Contact: Wen-Yi Tong, Binbin Chen E-mail:wytong@ee.ecnu.edu.cn;bbchen@phy.ecnu.edu.cn
  • Supported by:
    Project supported by the National Key R&D Program of China (Grant No. 2022YFA1402902), the National Natural Science Foundation of China (Grant Nos. 12374179, 12074119, 12374145, 051B22001, 12104157, 12134003, and 12304218), and the Shanghai Pujiang Program (Grant No. 23PJ1402200).

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摘要： The hybridization between oxygen 2p and transition-metal 3d states largely determines the electronic structure near the Fermi level and related functionalities of transition-metal oxides (TMOs). Considerable efforts have been made to manipulate the p-d hybridization in TMOs by tailoring the spatial orbital overlap via structural engineering. Here, we demonstrate enhanced p-d hybridization in Ba$^{2+}$-doped LaNiO$_{3}$ epitaxial films by simultaneously modifying both the spatial and energetic overlaps between the O-2p and Ni-3d orbitals. Combining x-ray absorption spectroscopy and first-principles calculations, we reveal that the enhanced hybridization stems from the synergistic effects of a reduced charge-transfer energy due to hole injection and an increased spatial orbital overlap due to straightening of Ni-O-Ni bonds. We further show that the enhanced p-d hybridization can be utilized to promote the oxygen evolution activity of LaNiO$_{3}$. This work sheds new insights into the fine-tuning of the electronic structures of TMOs for enhanced functionalities.

关键词: transition-metal oxide, doping, p-d hybridization, orbital overlap, oxygen evolution activity

Abstract: The hybridization between oxygen 2p and transition-metal 3d states largely determines the electronic structure near the Fermi level and related functionalities of transition-metal oxides (TMOs). Considerable efforts have been made to manipulate the p-d hybridization in TMOs by tailoring the spatial orbital overlap via structural engineering. Here, we demonstrate enhanced p-d hybridization in Ba$^{2+}$-doped LaNiO$_{3}$ epitaxial films by simultaneously modifying both the spatial and energetic overlaps between the O-2p and Ni-3d orbitals. Combining x-ray absorption spectroscopy and first-principles calculations, we reveal that the enhanced hybridization stems from the synergistic effects of a reduced charge-transfer energy due to hole injection and an increased spatial orbital overlap due to straightening of Ni-O-Ni bonds. We further show that the enhanced p-d hybridization can be utilized to promote the oxygen evolution activity of LaNiO$_{3}$. This work sheds new insights into the fine-tuning of the electronic structures of TMOs for enhanced functionalities.

Key words: transition-metal oxide, doping, p-d hybridization, orbital overlap, oxygen evolution activity

中图分类号:  (Defects and impurities in crystals; microstructure)

  • 61.72.-y
71.20.Be (Transition metals and alloys) 75.25.Dk (Orbital, charge, and other orders, including coupling of these orders) 82.45.-h (Electrochemistry and electrophoresis)