Bottom-up evolution of perovskite clusters into high-activity rhodium nanoparticles toward alkaline hydrogen evolution

Gaoxin Lin; Zhuang Zhang; Qiangjian Ju; Tong Wu; Carlo U Segre; Wei Chen; Hongru Peng; Hui Zhang; Qiunan Liu; Zhi Liu; Yifan Zhang; Shuyi Kong; Yuanlv Mao; Wei Zhao; Kazu Suenaga; Fuqiang Huang; Jiacheng Wang

doi:10.1038/s41467-023-35783-y

Bottom-up evolution of perovskite clusters into high-activity rhodium nanoparticles toward alkaline hydrogen evolution

Nat Commun. 2023 Jan 17;14(1):280. doi: 10.1038/s41467-023-35783-y.

Authors

Gaoxin Lin^#^{1

2}, Zhuang Zhang^#^{1

2}, Qiangjian Ju^#^{1

2}, Tong Wu^{1

2}, Carlo U Segre³, Wei Chen⁴, Hongru Peng⁵, Hui Zhang⁶, Qiunan Liu⁷, Zhi Liu^{5

6}, Yifan Zhang^{1

2}, Shuyi Kong^{1

2}, Yuanlv Mao^{1

2}, Wei Zhao^{1

2}, Kazu Suenaga⁷, Fuqiang Huang^{8

9}, Jiacheng Wang^{10

11

12

13}

Affiliations

¹ State Key Lab of High Performance Ceramics and Superfine microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 201899, Shanghai, China.
² Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, 100049, Beijing, China.
³ Department of Physics & Center for Synchrotron Radiation Research and Instrumentation, Illinois Institute of Technology, Chicago, IL, 60616, USA.
⁴ Department of Mechanical, Materials and Aerospace Engineering, Illinois Institute of Technology, Chicago, IL, 60616, USA.
⁵ School of Physical Science and Technology, ShanghaiTech University, 201210, Shanghai, China.
⁶ State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, 200050, Shanghai, China.
⁷ SANKEN, Osaka University, Ibaraki, 567-0047, Japan.
⁸ State Key Lab of High Performance Ceramics and Superfine microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 201899, Shanghai, China. huangfq@mail.sic.ac.cn.
⁹ State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, 100871, Beijing, China. huangfq@mail.sic.ac.cn.
¹⁰ State Key Lab of High Performance Ceramics and Superfine microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 201899, Shanghai, China. jiacheng.wang@mail.sic.ac.cn.
¹¹ Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, 100049, Beijing, China. jiacheng.wang@mail.sic.ac.cn.
¹² Hebei Provincial Key Laboratory of Inorganic Nonmetallic Materials, College of Materials Science and Engineering, North China University of Science and Technology, 063210, Tangshan, China. jiacheng.wang@mail.sic.ac.cn.
¹³ School of Materials Science and Engineering, Taizhou University, 318000, Taizhou, Zhejiang, China. jiacheng.wang@mail.sic.ac.cn.

^# Contributed equally.

Abstract

Self-reconstruction has been considered an efficient means to prepare efficient electrocatalysts in various energy transformation process for bond activation and breaking. However, developing nano-sized electrocatalysts through complete in-situ reconstruction with improved activity remains challenging. Herein, we report a bottom-up evolution route of electrochemically reducing Cs₃Rh₂I₉ halide-perovskite clusters on N-doped carbon to prepare ultrafine Rh nanoparticles (~2.2 nm) with large lattice spacings and grain boundaries. Various in-situ and ex-situ characterizations including electrochemical quartz crystal microbalance experiments elucidate the Cs and I extraction and Rh reduction during the electrochemical reduction. These Rh nanoparticles from Cs₃Rh₂I₉ clusters show significantly enhanced mass and area activity toward hydrogen evolution reaction in both alkaline and chlor-alkali electrolyte, superior to liquid-reduced Rh nanoparticles as well as bulk Cs₃Rh₂I₉-derived Rh via top-down electro-reduction transformation. Theoretical calculations demonstrate water activation could be boosted on Cs₃Rh₂I₉ clusters-derived Rh nanoparticles enriched with multiply sites, thus smoothing alkaline hydrogen evolution.

Grants and funding

92163117/National Natural Science Foundation of China (National Science Foundation of China)