Evoking ordered vacancies in metallic nanostructures toward a vacated Barlow packing for high-performance hydrogen evolution

Zhicheng Zhang; Guigao Liu; Xiaoya Cui; Yue Gong; Ding Yi; Qinghua Zhang; Chongzhi Zhu; Faisal Saleem; Bo Chen; Zhuangchai Lai; Qinbai Yun; Hongfei Cheng; Zhiqi Huang; Yongwu Peng; Zhanxi Fan; Bing Li; Wenrui Dai; Wei Chen; Yonghua Du; Lu Ma; Cheng-Jun Sun; Inhui Hwang; Shuangming Chen; Li Song; Feng Ding; Lin Gu; Yihan Zhu; Hua Zhang

doi:10.1126/sciadv.abd6647

Evoking ordered vacancies in metallic nanostructures toward a vacated Barlow packing for high-performance hydrogen evolution

Sci Adv. 2021 Mar 24;7(13):eabd6647. doi: 10.1126/sciadv.abd6647. Print 2021 Mar.

Authors

Zhicheng Zhang^{1

2}, Guigao Liu³, Xiaoya Cui², Yue Gong^{4

5

6}, Ding Yi⁷, Qinghua Zhang^{4

5

6}, Chongzhi Zhu^{8

9}, Faisal Saleem³, Bo Chen³, Zhuangchai Lai³, Qinbai Yun³, Hongfei Cheng², Zhiqi Huang³, Yongwu Peng^{2

10}, Zhanxi Fan^{3

11}, Bing Li¹², Wenrui Dai^{13

14

15}, Wei Chen^{13

14

15}, Yonghua Du¹⁶, Lu Ma¹⁶, Cheng-Jun Sun¹⁷, Inhui Hwang¹⁷, Shuangming Chen¹⁸, Li Song¹⁸, Feng Ding^{19

20}, Lin Gu^{21

5

6}, Yihan Zhu^{22

9}, Hua Zhang^{23

11}

Affiliations

¹ Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Department of Chemistry, School of Science, Tianjin University and Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 300072, China.
² Center for Programmable Materials, School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Singapore.
³ Department of Chemistry, City University of Hong Kong, Kowloon, Hong Kong, China.
⁴ Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China.
⁵ Collaborative Innovation Center of Quantum Matter, Beijing 100190, China.
⁶ School of Physical Sciences, University of Chinese Academy of Sciences, Beijing 100049, China.
⁷ Center for Multidimensional Carbon Materials, Institute for Basic Science (IBS), Ulsan 44919, Republic of Korea.
⁸ Center for Electron Microscopy and State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology, Zhejiang University of Technology, Hangzhou 310014, China.
⁹ College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, China.
¹⁰ College of Materials Science and Engineering, Zhejiang University of Technology, 18 Chaowang Road, Hangzhou, Zhejiang 310014, China.
¹¹ Hong Kong Branch of National Precious Metals Material Engineering Research Center (NPMM), City University of Hong Kong, Hong Kong, China.
¹² School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001, China.
¹³ Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore.
¹⁴ National University of Singapore (Suzhou) Research Institute, 377 Lin Quan Street¸ Suzhou Industrial Park, Jiang Su, 215123, China.
¹⁵ Department of Physics, National University of Singapore, 2 Science Drive 3, 117542, Singapore.
¹⁶ National Synchrotron Light Source II, Brookhaven National Laboratory, Upton, NY 11973, USA.
¹⁷ Advanced Photon Source, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439, USA.
¹⁸ National Synchrotron Radiation Laboratory, CAS Center for Excellence in Nanoscience, University of Science and Technology of China, Hefei 230029, China.
¹⁹ Center for Multidimensional Carbon Materials, Institute for Basic Science (IBS), Ulsan 44919, Republic of Korea. hua.zhang@cityu.edu.hk yihanzhu@zjut.edu.cn l.gu@iphy.ac.cn f.ding@unist.ac.kr.
²⁰ School of Materials Science and Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan 44919, Republic of Korea.
²¹ Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China. hua.zhang@cityu.edu.hk yihanzhu@zjut.edu.cn l.gu@iphy.ac.cn f.ding@unist.ac.kr.
²² Center for Electron Microscopy and State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology, Zhejiang University of Technology, Hangzhou 310014, China. hua.zhang@cityu.edu.hk yihanzhu@zjut.edu.cn l.gu@iphy.ac.cn f.ding@unist.ac.kr.
²³ Department of Chemistry, City University of Hong Kong, Kowloon, Hong Kong, China. hua.zhang@cityu.edu.hk yihanzhu@zjut.edu.cn l.gu@iphy.ac.cn f.ding@unist.ac.kr.

Abstract

Metallic nanostructures are commonly densely packed into a few packing variants with slightly different atomic packing factors. The structural aspects and physicochemical properties related with the vacancies in such nanostructures are rarely explored because of lack of an effective way to control the introduction of vacancy sites. Highly voided metallic nanostructures with ordered vacancies are however energetically high lying and very difficult to synthesize. Here, we report a chemical method for synthesis of hierarchical Rh nanostructures (Rh NSs) composed of ultrathin nanosheets, composed of hexagonal close-packed structure embedded with nanodomains that adopt a vacated Barlow packing with ordered vacancies. The obtained Rh NSs exhibit remarkably enhanced electrocatalytic activity and stability toward the hydrogen evolution reaction (HER) in alkaline media. Theoretical calculations reveal that the exceptional electrocatalytic performance of Rh NSs originates from their unique vacancy structures, which facilitate the adsorption and dissociation of H₂O in the HER.

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