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Solid–liquid–gas reaction accelerated by gas molecule tunnelling-like effect


Solid–liquid–gas reactions are ubiquitous and are encountered in both nature and industrial processes1,2,3,4. A comprehensive description of gas transport in liquid and following reactions at the solid–liquid–gas interface, which is substantial in regard to achieving enhanced triple-phase reactions, remains unavailable. Here, we report a real-time observation of the accelerated etching of gold nanorods with oxygen nanobubbles in aqueous hydrobromic acid using liquid-cell transmission electron microscopy. Our observations reveal that when an oxygen nanobubble is close to a nanorod below the critical distance (~1 nm), the local etching rate is significantly enhanced by over one order of magnitude. Molecular dynamics simulation results show that the strong attractive van der Waals interaction between the gold nanorod and oxygen molecules facilitates the transport of oxygen through the thin liquid layer to the gold surface and thus plays a crucial role in increasing the etching rate. This result sheds light on the rational design of solid–liquid–gas reactions for enhanced activities.

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Fig. 1: Schematic illumination of a solid–liquid–gas reaction established within a liquid cell.
Fig. 2: Real-time observation of Au nanorod etching process in the presence of O2 gas nanobubbles in a liquid cell.
Fig. 3: Real-time observation of Au nanorod etching with an O2 gas nanobubble at the nanorod end.
Fig. 4: Involvement of O2 gas in the Au nanorod etching pathway.

Data availability

The data that support the findings of this study are available from the corresponding authors upon request.


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This work is especially for the 120th anniversary of Southeast University. We thank H. Zhang and H.-T. Zhang (SEU-FEI Nano-Pico Center, Southeast University) for support and useful discussions. The work at Lawrence Berkeley National Laboratory was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division under contract no. DE-AC02-05-CH11231 within the in situ TEM programme (no. KC22ZH). The work at Southeast University was supported by the National Natural Science Foundation of China (grant nos. 51420105003, 11327901, 61601116 and 61974021) and the National Science Fund for Distinguished Young Scholars (grant no. 11525415). J.C. thanks the Natural Science Foundation of Shanghai (grant no. 14ZR1448100, 19ZR1463200), and the Shanghai Supercomputer Center of China and Big Data Science Center of Shanghai Synchrotron Radiation Facility. W.W. thanks the China Scholarship Council (no. 201806090114) for financial support.

Author information

Authors and Affiliations



W.W., H.F., H.Z. and L.S. conceived and designed the experiments. W.W. and T.X. performed the experiments. J.C., H.M., J.Y. and H.F. developed the simulations. J.S., H.D. and Q.Z. participated in discussions and data analysis. Z.G. and T.B. synthesized samples. L.S. supervised the project and revised the paper with H.Z. and H.F. The manuscript contains contributions by all authors. All authors gave approval to the final version of the manuscript.

Corresponding authors

Correspondence to Haiping Fang, Haimei Zheng or Litao Sun.

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The authors declare no competing interests.

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Nature Materials thanks Abhaya Datye and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–20.

Supplementary Video 1

Uniform etching of a Au nanorod without nanobubbles; electron dose rate was 780 e Å−2 s−1.

Supplementary Video 2

Etching of a Au nanorod with nanobubbles at the side; electron dose rate was 370 e Å−2 s−1.

Supplementary Video 3

Etching of a Au nanorod with a nanobubble at one end; electron dose rate was 370 e Å−2 s−1.

Supplementary Video 4

Etching of a Au nanorod with moving nanobubbles; electron dose rate was 200 e Å−2 s−1.

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Wang, W., Xu, T., Chen, J. et al. Solid–liquid–gas reaction accelerated by gas molecule tunnelling-like effect. Nat. Mater. (2022).

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