English

Epitaxial Growth of Unconventional 4H-Pd Based Alloy Nanostructures on 4H-Au Nanoribbons towards Highly Efficient Electrocatalytic Methanol Oxidation

• Jie Wang ^{1, 2, †,} ,
• Guigao Liu ^{2, 7, †,} ,
• Qinbai Yun ^3, ,
• Xichen Zhou ^3, ,
• Xiaozhi Liu ^6, ,
• Ye Chen ^8, ,
• Hongfei Cheng ^2, ,
• Yiyao Ge ^3, ,
• Jingtao Huang ^2, ,
• Zhaoning Hu ^2, ,
• Bo Chen ^3, ,
• Zhanxi Fan ^{3, 4, 5,} ,
• Lin Gu ^9, ,
• Hua Zhang ^{3, 4, 5, ,}

• 1.

  Key Laboratory of Fluid and Power Machinery of Ministry of Education, School of Materials Science and Engineering, Xihua University, Chengdu 610039, China

• 2.

  Center for Programmable Materials, School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798, Singapore

• 3.

  Department of Chemistry, City University of Hong Kong, Hong Kong, China

• 4.

  Hong Kong Branch of National Precious Metals Material Engineering Research Center (NPMM), City University of Hong Kong, Hong Kong, China

• 5.

  Shenzhen Research Institute, City University of Hong Kong, Shenzhen 518057, Guangdong Province, China

• 6.

  Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China

• 7.

  National Special Superfine Powder Engineering Research Center, School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China

• 8.

  Department of Chemistry, The Chinese University of Hong Kong, Hong Kong, China

• 9.

  Beijing National Center for Electron Microscopy and Laboratory of Advanced Materials, Department of Materials Science and Engineering, Tsinghua University, Beijing 100084, China

• ^†These authors contributed equally to this work.

Corresponding author: Hua Zhang, hua.zhang@cityu.edu.hk

• Received Date: 17 May 2023
  Accepted Date: 10 July 2023
  Revised Date: 09 July 2023
  Available Online: 15 October 2023
• Fund Project:

Abstract: Direct methanol fuel cells (DMFCs) hold great promise as clean energy conversion devices in the future. Noble metal nanocatalysts, renowned for their exceptional catalytic activity and stability, play a crucial role in DMFCs. Among these catalysts, Pt- and Pd-based nanocatalysts are widely recognized as the most effective catalysts for the electrochemical methanol oxidation reaction (MOR), which is the key half-cell reaction in DMFCs. However, due to the high cost of Pt- and Pd-based materials, there is a strong desire to further enhance their catalytic performance. One of the most promising approaches for it is to develop noble metal-based alloy nanocatalysts, which have shown great potential in improving electrocatalytic activity. Notably, advancements in phase engineering of nanomaterials (PEN) have revealed that noble metal-based nanomaterials with unconventional phases exhibit superior catalytic properties in various catalytic reactions compared to their counterparts with conventional phases. To obtain noble metal-based nanocatalysts with unconventional crystal phases, wet-chemical epitaxial growth has been employed as a facile and effective method, utilizing unconventional-phase noble metal nanocrystals as templates. Nevertheless, epitaxially growing bimetallic alloy nanostructures with unconventional crystal phases remains a challenge, impeding further exploration of their catalytic performance in electrochemical reactions such as MOR. In this study, we utilize 4H hexagonal phase Au (4H-Au) nanoribbons as templates for the epitaxial growth of unconventional 4H hexagonal PdFe, PdIr, and PdRu, resulting in the formation of 4H-Au@PdM (M = Fe, Ir, and Ru) core-shell nanoribbons. As a proof-of-concept application, we investigate the electrocatalytic activity of the synthesized 4H-Au@PdFe nanoribbons towards MOR, which exhibit a mass activity of 3.69 A·mg_Pd⁻¹, i.e., 10.5 and 2.4 times that of Pd black and Pt/C, respectively, placing it among the best Pd- and Pt-based MOR electrocatalysts. Our strategy opens up an avenue for the rational construction of unconventional-phase multimetallic nanostructures to explore their phase-dependent properties in various applications.

Key words:
• Phase engineering of nanomaterials
•  /  Crystal phase
•  /  4H phase
•  /  Pd-based alloy
•  /  Methanol oxidation reaction

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