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Dynamic shrinkage of metal-oxygen bonds in atomic Co-doped nanoporous RuO2 for acidic oxygen evolution

原子级Co掺杂纳米多孔RuO2催化剂中金属-氧配体 键的动态收缩加速酸性氧析出反应

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Abstract

The design of highly active and stable catalysts for the oxygen evolution reaction (OER) in acidic media has become an attractive research area for the development of energy conversion and storage technologies. However, progress in this area has been limited by the poor understanding of the dynamic active structure of catalysts under realistic OER conditions. Here, an atomic Co-doped nanoporous RuO2 electrocatalyst, which exhibited excellent OER activity and stability in acidic conditions, was synthesized through annealing and etching of a nanoporous Co-Ru alloy. Operando X-ray absorption spectroscopy results confirmed that the etching strategy produced abundant oxygen vacancies around the metal centers in the atomic Co-doped nanoporous RuO2 electrocatalyst. These vacancies created contracted metal-oxygen ligand bonds under realistic OER conditions. The dynamic structural evolution of the synthesized electrocatalyst allowed them to experience lower kinetic barriers during OER catalysis, resulting in enhanced catalytic activity and stability. This study also provided atomic details on the active structure of the electrocatalyst and the influence of their structural evolution on OER activity.

摘要

设计在酸性介质中具有高活性和高稳定性的氧析出反应(OER) 催化剂对能量转换和储存技术的发展具有重要意义. 然而, 在实际OER 条件下催化剂的原子结构会发生变化, 且目前对其动态活性结构的认 识仍然不足. 本文中, 我们通过退火和蚀刻纳米多孔Co-Ru合金合成了 具有优异酸性OER活性和稳定性的原子级Co掺杂纳米多孔RuO2催化 剂. 原位X射线吸收光谱证实: 蚀刻策略可以在原子级Co掺杂纳米多孔 RuO2的金属中心周围产生丰富的氧空位, 从而在实际OER条件下产生 收缩的金属-氧配体键. 这种动态结构演变降低了催化活性位点在OER 过程中的动力学势垒, 因而催化剂的催化活性和稳定性大幅提高. 本研 究结果揭示了催化剂活性结构的原子细节以及它们的结构演化对催化 活性的影响.

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Acknowledgements

The authors acknowledge the support from the National Natural Science Foundation of China (51771072), the Outstanding Youth Scientist Foundation of Hunan Province (2020JJ2006), the Fundamental Research Funds for the Central Universities, and the State Key Laboratory of Advanced Design and Manufacturing for Vehicle Body Independent Research Project (71860007). The authors also thank Dr. Ying-Rui Lu and Prof. Ting-Shan Chan for the XAS measurement at Taiwan Light Source.

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Author notes

  1. These authors contributed equally to the work.

Authors and Affiliations

  1. College of Materials Science and Engineering, State Key Laboratory of Advanced Design and Manufacturing for Vehicle Body, Hunan University, Changsha, 410082, China

    Qiuli Wu  (吴秋丽), Kang Jiang  (蒋康), Dechao Chen  (陈德超), Jiao Lan  (蓝蛟), Ming Peng  (彭鸣) & Yongwen Tan  (谭勇文)

  2. Advanced Institute for Materials Research, Tohoku University, Sendai, 980-8577, Japan

    Jiuhui Han  (韩久慧)

  3. School of Electronic Information Engineering, Wuxi University, Wuxi, 214105, China

    Min Luo  (罗敏)

Authors
  1. Qiuli Wu  (吴秋丽)
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  2. Kang Jiang  (蒋康)
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  3. Jiuhui Han  (韩久慧)
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  5. Min Luo  (罗敏)
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  7. Ming Peng  (彭鸣)
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  8. Yongwen Tan  (谭勇文)
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Contributions

Tan Y conceived and supervised this study; Wu Q, Jiang K, Chen D and Lan J carried out the fabrication and characterizations of materials, and electrochemical measurements; Han J conducted the TEM characterizations; Jiang K and Peng M contributed to the XAS measurements and analyses; Tan Y, Jiang K, and Wu Q wrote the paper. All authors contributed to discussions and manuscript review.

Corresponding author

Correspondence to Yongwen Tan  (谭勇文).

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Conflict of interest

The authors declare no conflict of interest.

Supplementary information

Experimental details and supporting data are available in the online version of the paper.

Qiuli Wu received her MSc degree from Hunan University under the supervisor of Prof. Tan in 2020. Her research interests mainly focus on the preparation and application of nanoporous materials.

Kang Jiang is currently a PhD student under the supervisor of Prof. Tan at the College of Materials Science and Engineering, Hunan University. He received his BE degree from Hunan University in 2018. His current research focuses on the design of 3D nanoporous materials and their applications in electrocatalytic water splitting.

Yongwen Tan is a full professor at the College of Materials Science and Engineering, Hunan University. He received his PhD degree from the College of Materials Science and Engineering, Shanghai Jiao Tong University, China, in 2013. Then, he joined the Advanced Institute for Materials Research (AIMR), Tohoku University as a research associate. His research focuses on the synthesis and applications of 3D nanoporous materials.

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Wu, Q., Jiang, K., Han, J. et al. Dynamic shrinkage of metal-oxygen bonds in atomic Co-doped nanoporous RuO2 for acidic oxygen evolution. Sci. China Mater. 65, 1262–1268 (2022). https://doi.org/10.1007/s40843-021-1912-8

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  • DOI: https://doi.org/10.1007/s40843-021-1912-8

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