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Surface composition-tunable octahedral PtCu nanoalloys advance the electrocatalytic performance on methanol and ethanol oxidation

  • Fengling Zhao (赵凤玲)
  • Qiang Yuan (袁强)Email author
  • Bin Luo (罗斌)
  • Chaozhong Li (李朝忠)
  • Fang Yang (杨芳)
  • Xiaotong Yang (杨晓彤)
  • Zhiyou Zhou (周志有)
Articles

Abstract

The synthesis of surface composition-tunable Pt-based octahedral nanoalloys is key to unravel the structure-property relationship in fuel cells. Herein, we report a facile route to prepare composition-tunable PtCu octahedral nanoalloys by using halogen ions (Br- or/and I-) as composition modulators. Among these PtCu octahedral nanoalloys, Pt59Cu41 octahedron exhibits the highest catalytic activity and durability in alkaline solution. The specific activity/mass activity of Pt59Cu41 octahedron is 20.25 mA cm-2/3.24 A mg-1Pt, which is 6.64/5.3 times higher than commercial Pt black in 0.5 mol L-1 CH3OH, respectively. In the case of using ethanol (0.5 mol L-1) as fuel source, Pt59Cu41 octahedron shows much better catalytic activity, that is 34.84 mA cm-2/5.58 A mg-1Pt for specific activity/mass activity, which is 9.16/7.34 times higher than commercial Pt black, respectively. In situ Fourier transform infrared spectroscopy is employed to detect the intermediate species and products for methanol/ethanol oxidation reaction and a plausible mechanism is proposed to explain the improved activity and durability of Pt59Cu41 octahedron toward methanol/ethanol oxidation in alkaline medium.

Key words

octahedral PtCu alloy composition and strain-tunable in situ FTIR direct methanol/ethanol fuel cells 

表面组成和应变可调的PtCu八面体纳米合金促进甲醇和乙醇电催化性能

摘要

本文介绍了一种以卤素离子(Br−或/和I−)为成分调变剂制备 组成和应变可调的PtCu八面体纳米合金的简便方法. 由于纳米合 金化所产生的配位效应、协同效应和应变效应, PtCu八面体纳米 合金在碱性介质中对甲醇和乙醇电氧化表现出优于商业Pt黑的催 化性能. 在这些PtCu八面体纳米合金中, 优化的Pt59Cu41八面体纳 米合金具有较高的催化活性和耐久性. 对于甲醇氧化, Pt59Cu41八 面体的比活性/质量活性为20.25 mA cm−2/3.24 A mg−1Pt, 分别是商 业铂黑的6.64/5.3倍. 对于乙醇氧化, Pt59Cu41八面体的比活性/质量 活性为34.84 mA cm−2/5.58 A mg−1Pt, 分别是商业铂黑的9.16/7.34 倍. 利用原位傅立叶变换红外光谱技术, 对甲醇/乙醇氧化反应中 的中间物种和产物进行了检测, 并探讨了Pt59Cu41八面体催化活性 和耐久性较好的原因, 同时解释了在碱性介质中甲醇氧化耐久性 优于乙醇的原因. 本文对探索制备高性能的碱性甲醇/乙醇燃料电 池纳米电催化剂具有一定的科学意义.

Notes

Acknowledgements

This work was supported by the National Natural Science Foundation of China (21571038 and 21361005), the Open Fund of the Key Lab of Organic Optoelectronics & Molecular Engineering (Tsinghua University), the Foundation for Excellent Young Scientific and Technological Talents of Guizhou Province (2019-5666) and the Special Fund for Natural Science of Guizhou University (201801). We also appreciate Prof. Xun Wang (Tsinghua University) for HRTEM experiments.

Supplementary material

40843_2019_9460_MOESM1_ESM.pdf (597 kb)
Supplementary material, approximately 228 KB.

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Copyright information

© Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Fengling Zhao (赵凤玲)
    • 1
  • Qiang Yuan (袁强)
    • 1
    • 2
    Email author
  • Bin Luo (罗斌)
    • 1
  • Chaozhong Li (李朝忠)
    • 1
  • Fang Yang (杨芳)
    • 1
  • Xiaotong Yang (杨晓彤)
    • 1
  • Zhiyou Zhou (周志有)
    • 3
  1. 1.Department of Chemistry, College of Chemistry and Chemical EngineeringGuizhou UniversityGuiyangChina
  2. 2.Key Lab of Organic Optoelectronics & Molecular EngineeringTsinghua UniversityBeijingChina
  3. 3.State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical EngineeringXiamen UniversityXiamenChina

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