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Rational electrochemical design of hierarchical microarchitectures for SERS sensing applications

Nature Synthesis volume 3, pages 867–877 (2024)Cite this article

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Abstract

Electrochemical deposition has been widely used to prepare conformal coatings but has rarely been used to design well-defined micro/nanostructures. Here we report electrochemical synthesis of complex, hierarchical inorganic microarchitectures simply via programming the applied potential waveforms. We identify two distinct electrochemical growth modes—the stacking mode and the flattening mode—under different potential waveforms. We demonstrate how these growth modes can work individually or cooperatively to design previously inaccessible microarchitectures. Each specific potential waveform corresponds to a specific microarchitecture, allowing us to prepare a rich library of microarchitectures. The designed microarchitectures can be converted into other materials by simple redox-potential-driven chemical reactions. We preliminarily studied the applications of converted nanoporous silver microscale torpedoes as high-performance surface-enhanced Raman spectroscopy (SERS) sensing substrates. The reported method opens up a new concept to design complex inorganic microarchitectures with promising applications in metamaterials, chemically or magnetically propelled microrobotics, and miniaturized devices.

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Fig. 1: The concept and physical mechanism of the electrochemical method used to construct complex microarchitectures.
Fig. 2: Designing Ag7O8NO3 microarchitectures via the stacking and flattening electrochemical growth modes.
Fig. 3: Design of microarchitectures using gradually increasing potential waveforms.
Fig. 4: Design of microscale torpedoes using gradually decreasing potential waveforms and a selective peeling-off process.
Fig. 5: Microscale torpedoes with different numbers of joints selectively peeled off from the electrode surface.
Fig. 6: The design of complex microarchitectures using complex potential waveforms.
Fig. 7: SERS sensing performance of nanoporous silver microscale torpedoes transformed from Ag7O8NO3 microscale torpedoes.
Fig. 8: Morphology-preserving transformation of the Ag7O8NO3 microarchitectures into other metal oxides driven by the redox potential differences.

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Acknowledgements

We acknowledge funding support from the Key R&D Program of Zhejiang Province (2023C01088), the National Natural Science Foundation of China (52273233 and 51971200), the Zhejiang Provincial Natural Science Foundation of China (LR19E010001) and the Open Research Program of Key Laboratory of 3D Micro/Nano Fabrication and Characterization of Zhejiang Province, Westlake University. Part of the work was conducted in the ZJU micro-nanofabrication center.

Author information

Author notes

  1. These authors contributed equally: Liyan Zhao, Yanling Wang, Shoutong Jin.

Authors and Affiliations

  1. Department of Medical Oncology, The First Affiliated Hospital, Zhejiang University School of Medicine, Hangzhou, China

    Liyan Zhao, Xiaochen Zhang & Shikuan Yang

  2. School of Materials Science and Engineering, Zhejiang University, Hangzhou, China

    Liyan Zhao, Yanling Wang, Shoutong Jin, Ning An, Mi Yan, Zijian Hong & Shikuan Yang

  3. State Key Laboratory of Baiyunobo Rare Earth Resource Researches and Comprehensive Utilization, Baotou Research Institution of Rare Earths, Baotou, China

    Mi Yan & Shikuan Yang

  4. Zhejiang Key Laboratory of Advanced Solid State Energy Storage Technology and Applications, Taizhou Institute of Zhejiang University, Taizhou, China

    Zijian Hong

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Contributions

S.Y. and L.Z. conceived the idea and designed the study. L.Z., Y.W. and N.A. carried out the materials synthesis and characterizations. S.J. and Z.H. performed the phase-field simulations. L.Z., M.Y., X.Z., Z.H. and S.Y. analysed the data. L.Z., M.Y., Z.H. and S.Y. wrote the paper. All authors contributed to the revision of the paper.

Corresponding authors

Correspondence to Mi Yan, Zijian Hong or Shikuan Yang.

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The authors declare no competing interests.

Peer review

Peer review information

Nature Synthesis thanks Domenica Tonelli, Yexiang Tong and Jon Ustarroz for their contribution to the peer review of this work. Primary Handling Editor: Alexandra Groves, in collaboration with the Nature Synthesis team.

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Supplementary information

Supplementary Information

Supplementary discussion, captions for Videos 1–5 and Figs. 1–34.

Supplementary Video 1

The microarchitecture design concept: the morphology evolvement of the microarchitectures as the potential waveform changes.

Supplementary Video 2

The change of the ion concentration distribution and the corresponding morphology change when applying 0.18 V to a preformed micropyramid and when the potential is increased from 0.18 V to 0.22 V simulated by the phase-field method.

Supplementary Video 3

The change of the ion concentration distribution and the corresponding morphology change when applying 0.12 V to a preformed binary microarchitecture simulated by the phase-field method.

Supplementary Video 4

Selectively peeling off the uniformly structured microscale torpedoes from the electrode surface by slowly immersing it into water.

Supplementary Video 5

The moving behavior of Ag7O8NO3 microscale torpedoes in 2.5 wt.% H2O2 aqueous solutions.

Source data

Source Data Fig. 1

Unprocessed statistical source data for Fig. 1.

Source Data Fig. 4

Unprocessed statistical source data for Fig. 4.

Source Data Fig. 5

Unprocessed statistical source data for Fig. 5.

Source Data Fig. 7

Unprocessed statistical source data for Fig. 7.

Source Data Fig. 8

Unprocessed statistical source data for Fig. 8.

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Zhao, L., Wang, Y., Jin, S. et al. Rational electrochemical design of hierarchical microarchitectures for SERS sensing applications. Nat. Synth 3, 867–877 (2024). https://doi.org/10.1038/s44160-024-00553-1

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