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SCIENCE CHINA Materials, Volume 64 , Issue 10 : 2454-2466(2021) https://doi.org/10.1007/s40843-020-1635-9

Tailoring lattice strain in ultra-fine high-entropy alloys for active and stable methanol oxidation

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  • ReceivedDec 31, 2020
  • AcceptedFeb 3, 2021
  • PublishedMay 14, 2021

Abstract


Funded by

the National Natural Science Foundation of China(51402100,21573066,21825201,22002039,21522305)

the Scientific Research Foundation of Hunan Provincial Education Department(19C0054)

the Postgraduate Scientific Research Innovation Project of Hunan Province(CX20200441)

the Australian Research Council(CE,140100012)

and Compute Canada

Natural Sciences and Engineering Research Council of Canada(NSERC)

University of Toronto.


Acknowledgment

This work was supported by the National Natural Science Foundation of China (51402100, 21573066, 21825201, 22002039, and 21522305), the Scientific Research Foundation of Hunan Provincial Education Department (19C0054), the Postgraduate Scientific Research Innovation Project of Hunan Province (CX20200441), the Australian Research Council (CE 140100012)| the Australian National Fabrication Facility | UOW Electron Microscopy Centre, and Compute Canada, Natural Sciences and Engineering Research Council of Canada (NSERC), University of Toronto.


Interest statement

The authors declare that they have no conflict of interest.


Contributions statement

Wang S, Singh CV, Tao L, Zhang Y, Chen J and Dong CL conceived the idea and directed the research. Wang D, Chen Z, Huang YC and Li W designed the experiments. Wang D, Li W, Wang J, Gu K, Huang X, Chen J and Wang T synthesized the materials and carried out the XRD, XPS, TEM and STEM physical characterizations. Huang Y and Dong CL did the XANES and EXAFS experiments. Wang D, Zhang Y, Wu Y and Chen C completed the electrochemical tests. Chen Z, Lu Z and Singh CV provided the DFT calculation for this work. Wang D, Chen Z, Huang YC and Li W wrote the paper with comments from all authors.


Author information

Dongdong Wang received his Bachelor degree in 2018 from Hunan University of Science and Technology, China. He is currently pursuing his PhD degree under the supervision of Prof. Shuangyin Wang at Hunan University. His research interest includes the synthesis, characterization of nanomaterials for electrocatalysis and electrochemical coupling.


Zhiwen Chen works as a postdoctoral fellow in the Department of Materials Science and Engineering (MSE) at the University of Toronto, Canada. He received his PhD degree from Jilin University, China. His current research focuses on the catalyst design for hydrogen evolution reaction, CO2 reduction reaction, nitrogen reduction reaction, etc. through density functional theory calculations. Some of his studies are carried out in close collaboration with experiments.


Yu-Cheng Huang received his BSc degree from Tamkang University in 2015, and obtained his MSc degree in the Department of Electrophysics from Chiao Tung University in 2017. He started studying for PhD in the Department of Electrophysics, Chiao Tung University in 2017. His research focuses on fundamental XAS analysis, including XANES, EXAFS and soft X-ray in-situ measurement techniques.


Wei Li received his BSc degree in 2013 from Huazhong Agricultural University and his PhD degree in 2018 from Chongqing University under the supervision of Prof. Zidong Wei. He currently works at Hunan University as a postdoctoral researcher under the co-supervision of Prof. Shuangyin Wang. His main research focuses on the development of defective nanomaterials in fuel cell application.


Yiqiong Zhang received her Master degree in 2015 from South China Normal University and her PhD degree in 2019 from Hunan University under the supervision of Prof. Shuangyin Wang. She is currently working at the College of Materials Science and Engineering, Changsha University of Science &Technology. Her current research interests include the synthesis and characterization of nanomaterials with various defects for electrochemical energy conversion and storage technologies.


Li Tao received his Master degree in 2016 and his PhD degree in 2019 from Hunan University under the supervision of Prof. Shuangyin Wang. He is currently an assistant professor of the key Laboratory for Graphene Materials and Devices and College of Chemistry and Chemical Engineering, Hunan University. His research interests are in plasma technology, defect chemistry and fuel cell.


Chung-Li Dong received his PhD degree in physics from Tamkang University in 2004. He then worked as a postdoctoral fellow at the Advanced Light Source Facility (Lawrence Berkeley National Laboratory) with Prof. Jinghua Guo. Now he joined the Department of Physics at Tamkang University as Associate Professor. His current research interests include the development of electrochromic, gaschromic and thermochromic related soft/hard X-ray in-situ reactors, lithium battery systems, supercapacitor systems, and electrocatalytic hydrogen production catalysts.


Jun Chen received his PhD degree at the School of Chemistry, University of Wollongong, Australia, in 2003. Professor Chen is a Chief Investigator of The ARC Centre of Excellence for Electromaterials Science (ACES). His research interests include sustainable energy devices/systems, electro-/bio- interfaces, nano/micro-materials, 2D/3D printing, and design and fabrication of smart electronic devices.


Chandra Veer Singh is the Erwin Edward Hart Endowed Associate Professor and Associate Chair of Research in the Department of Materials Science and Engineering at the University of Toronto, Canada. Dr Singh received his PhD degree in aerospace engineering from Texas A&M University. Subsequently, he worked as a postdoctoral fellow at Cornell University. His research is currently focused on the atomistic modeling and machine learning enabled development of new materials for catalysts and metal-ion batteries.


Shuangyin Wang received his BSc degree in 2006 from Zhejiang University and his PhD degree in 2010 from Nanyang Technological University, Singapore. He is currently a professor of the Key Laboratory for Graphene Materials and Devices and College of Chemistry and Chemical Engineering, Hunan University. His research interests are in plasma technology, defects in various crystals and their application for electrochemical energy storage and conversion.


Supplement

Supplementary information

Supporting data are available in the online version of the paper.


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  • Figure 1

    Structural, morphological, and elemental characterizations. (a) Schematic diagram of the transformation from pure metal element FCC structure to HEAs FCC structure. (b) The XRD patterns of HEA-400 and HEA-700. (c) STEM-EDS spectrum, (d, e) TEM images, (f) high-resolution STEM image, and (g) STEM-EDS elemental mapping of HEA-400. (h, i) TEM images, (j) high-resolution STEM image, and (k) STEM-EDS elemental mapping of HEA-700.

  • Figure 2

    Local structure analyses. (a) Pt 4f XPS spectra of HEAs. Surface valence band photoemission spectra of (b) HEA-400 and (c) HEA-700.(d) Pt L3-edge XANES of HEAs as well as the reference samples. Inset shows the enlarged spectra at Pt L3-edge. The Fourier transform (FT) of the EXAFS spectra of HEAs as well as the reference samples: (e) Pt L3-edge, (f) Fe K-edge, (g) Co K-edge, (h) Ni K-edge, and (i) Cu K-edge.

  • Figure 3

    Electrocatalytic performance. (a) Cyclic voltammograms of Pt/C, HEA-400 and HEA-700 catalysts in N2-saturated 0.1 mol L−1 HClO4 solution at a scan rate of 50 mV s−1. (b) Electrocatalytic activities of Pt/C, HEA-400 and HEA-700 catalysts in N2-saturated 1 mol L−1 CH3OH + 0.1 mol L−1 HClO4 solution at a scan rate of 50 mV s−1. (c) Specific activities and mass activities of Pt/C, HEA-400 and HEA-700 catalysts. (d) CO stripping voltammograms of HEA-700, HEA-400, and Pt/C catalysts in 0.1 mol L−1 HClO4 solution. (e) Chronoamperometric curves of the Pt/C, HEA-400 and HEA-700 catalysts in 1 mol L−1 CH3OH + 0.1 mol L−1 HClO4 solution at 0.60 V for 5000 s. (f) In operando Nyquist plots of EIS for MOR on HEA-700 catalyst at 0.25–0.65 V. The inset shows Nyquist plots at 0–0.20 V, where the applied voltage is referenced to the SCE.

  • Figure 4

    DFT calculations. (a) Geometrically optimized atomic structures of Pt(111), HEA-400 and HEA-700. Sliver, yellow, purple, pink, and blue balls represent Pt, Fe, Co, Ni, and Cu atoms. The small sliver balls indicate the surface Pt atoms. (b) Adsorption energies of CO on Pt(111), HEA-400 and HEA-700. (c) d-Orbitals of surface Pt atoms in the systems of Pt(111), HEA-400 and HEA-700. The dotted line represents the d-band centers.

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