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A universal approach for the synthesis of mesoporous gold, palladium and platinum films for applications in electrocatalysis

Nature Protocols volume 15, pages 2980–3008 (2020)Cite this article

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Abstract

High-surface-area mesoporous materials expose abundant functional sites for improved performance in applications such as gas storage/separation, catalysis, and sensing. Recently, soft templates composed of amphiphilic surfactants and block copolymers have been used to introduce mesoporosity in various materials, including metals, metal oxides and carbonaceous compounds. In particular, mesoporous metals are attractive in electrocatalysis because their porous networks expose numerous unsaturated atoms on high-index facets that are highly active in catalysis. In this protocol, we describe how to create mesoporous metal films composed of gold, palladium, or platinum using block copolymer micelle templates. The amphiphilic block copolymer micelles are the sacrificial templates and generate uniform structures with tunable pore sizes in electrodeposited metal films. The procedure describes the electrodeposition in detail, including parameters such as micelle diameters, deposition potentials, and deposition times to ensure reproducibility. The micelle diameters can be controlled by swelling the micelles with different solvent mixtures or by using block copolymer micelles with different molecular weights. The deposition potentials and deposition times allow further control of the mesoporous structure and its thickness, respectively. Procedures for example applications are included: glucose oxidation, ethanol oxidation and methanol oxidation reactions. The synthetic methods for preparation of mesoporous metal films will take ~4 h; the subsequent electrochemical tests will take ~5 h for glucose sensing and ~3 h for alcohol oxidation reaction.

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Fig. 1: Pictures of the whole mesoporous fabrication process.
Fig. 2: Schematic illustrations of the whole mesoporous fabrication process from micelle formation to mesoporous metal formation.
Fig. 3: Process flow used to determine the diameter distributions of block copolymer micelles.
Fig. 4: Thickness and ECSA changes with deposition times.
Fig. 5
Fig. 6: Dependence of pore size distribution of MGFs on hydrophobic organic compound.
Fig. 7: Dependence of pore size distributions in the MGFs on the molecular weights of the block copolymers.
Fig. 8
Fig. 9: Pore size distributions of MPdFs using block copolymers with different molecular weights.
Fig. 10: Pore size distributions of MPtFs using block copolymers with different molecular weights.
Fig. 11: Glucose sensing using MGFs.
Fig. 12: The results of EOR and MOR applications using MPdFs and MPtFs.

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Acknowledgements

H.L. and K.K. are funded by The University of Queensland Research and Training Program. This work was performed in part at the Queensland node of the Australian National Fabrication Facility (ANFF-Q), a company established under the National Collaborative Research Infrastructure Strategy to provide nano- and micro-fabrication facilities for Australia’s researchers. The authors acknowledge the facilities, and the scientific and technical assistance, of the Australian Microscopy & Microanalysis Research Facility at the Centre for Microscopy and Microanalysis, The University of Queensland. This work is also supported by the Korea Institute of Industrial Technology (KITECH, JE200017).

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Author notes

  1. These authors contributed equally: Hyunsoo Lim, Kenya Kani.

Authors and Affiliations

  1. Australian Institute for Bioengineering and Nanotechnology (AIBN), The University of Queensland, Brisbane, Australia

    Hyunsoo Lim, Kenya Kani, Tomota Nagaura, Asep Sugih Nugraha, Md. Shahriar A. Hossain, Alan E. Rowan, Jongbeom Na & Yusuke Yamauchi

  2. International Center for Materials Nanoarchitechtonics (WPI-MANA), National Institute for Materials Science (NIMS), Tsukuba, Japan

    Joel Henzie, Muhammad Iqbal, Yoshio Bando, Jongbeom Na & Yusuke Yamauchi

  3. Institute of Molecular Plus, Tianjin University, Tianjin, People’s Republic of China

    Muhammad Iqbal & Yoshio Bando

  4. Korea Biochar Research Center & Division of Environmental Science and Ecological Engineering, Korea University, Seoul, Republic of Korea

    Yong Sik Ok

  5. School of Mechanical & Mining Engineering, The University of Queensland, Brisbane, Australia

    Md. Shahriar A. Hossain

  6. Australian Institute of Innovative Materials (AIIM), University of Wollongong, North Wollongong, Australia

    Yoshio Bando

  7. Department of Chemical Engineering, National Taiwan University, Taipei, Taiwan

    Kevin C. W. Wu

  8. Surface Technology Group, Korea Institute of Industrial Technology (KITECH), Incheon, Republic of Korea

    Hyun-Jong Kim

  9. School of Chemical Engineering, The University of Queensland, Brisbane, Australia

    Yusuke Yamauchi

  10. Department of Plant & Environmental New Resources, Kyung Hee University, Yongin-si, Gyeonggi-do, South Korea

    Yusuke Yamauchi

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  1. Hyunsoo Lim
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Contributions

Y.Y. and J.N. proposed the research direction and guided the project. Y.Y., J.N., and Y.B. developed the protocol. H.L. and K.K. performed the experiments. H.L., K.K., and J.H. drafted the manuscript. J.H., T.N., A.S.N., Y.S.O., and K.C.W.W. analyzed morphologies. M.I., M.S.A.H., A.E.R., and H.-J.K. did formal analysis. All authors contributed to the manuscript.

Corresponding authors

Correspondence to Jongbeom Na or Yusuke Yamauchi.

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Peer review information Nature Protocols thanks Xiaoguo Liu, Liang Wang and Dongyuan Zhao for their contribution to the peer review of this work.

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Key references using this protocol

Li, C. et. al. Nat. Commun. 6, 6608 (2015): https://www.nature.com/articles/ncomms7608

Iqbal, M. et. al. Nanoscale Horiz. 4, 960–968 (2019): https://pubs.rsc.org/en/content/articlelanding/2019/nh/c8nh00507a#!divAbstract

Nugraha, A. S., et. al. ChemElectroChem 4, 2571–2576 (2017): https://doi.org/10.1002/celc.2017005

Key data used in this protocol

Li, C. et. al. Nat. Commun. 6, 6608 (2015): https://www.nature.com/articles/ncomms7608

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Supplementary Table 1 and Supplementary Figs. 1 and 2.

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Lim, H., Kani, K., Henzie, J. et al. A universal approach for the synthesis of mesoporous gold, palladium and platinum films for applications in electrocatalysis. Nat Protoc 15, 2980–3008 (2020). https://doi.org/10.1038/s41596-020-0359-8

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