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Solid–liquid phase transition induced electrocatalytic switching from hydrogen evolution to highly selective CO2 reduction

Nature Catalysis volume 4, pages 202–211 (2021)Cite this article

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A Publisher Correction to this article was published on 01 April 2021

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Abstract

Conventional strategies for modifying electrocatalysts for efficient CO2 reduction are mainly based on doping, defect/morphology engineering, substrate design and so on. In most cases, these methods can only tune their structures, electronic states and thereby catalytic properties in a gradual way. Here we report that the solid–liquid phase transition of Ga–Sn/Ga–In alloys can induce an instant and radical transformation of their atomic and electronic structures during electrocatalysis, which dramatically impacts their catalytic properties. The transition of Sn/In active components from phase-segregated clusters to dispersed single atoms during melting results in a unique electronic structure through further reduction of both metallic Sn/In and Ga. Such atomic/electronic structure transitions can correlate well with suppression of the hydrogen evolution reaction and an enhanced formate Faradaic efficiency from <35% to >95%. This two-state switching strategy may be extended to other catalytic reactions to determine correlations between their structures and catalytic properties.

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Fig. 1: The impact of solid–liquid phase transition on the properties of Ga–Sn/Ga–In alloys.
Fig. 2: Electrochemical CO2 reduction with Ga–Sn alloy.
Fig. 3: In situ Sn K-edge XAS spectra of Ga–Sn alloy during CO2 electroreduction.
Fig. 4: Temperature-dependent STEM images, SAED patterns and EDS mappings of Ga–Sn alloy.
Fig. 5: Atomic and electronic structure evolutions studied by XPS and XANES fitting.
Fig. 6: Stability tests of Ga–Sn alloy for CO2 electroreduction.

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Data availability

The most essential electrochemical, catalytic, XAS and XPS data are shared on figshare and can be accessed via https://doi.org/10.6084/m9.figshare.13347812.v4. The rest of the data that support the plots within this paper and the other findings of this study are available from the corresponding authors upon reasonable request. The XAS data are also available from the BL14W1 beamline station at the Shanghai Synchrotron Radiation Facility. The atomic coordinate data for the ab initio molecular dynamic simulations are included in Supplementary Data 1. The videos relevant to the appearance of the liquid Ga–Sn electrode and its solid–liquid phase transitions during CO2 electroreduction are provided as Supplementary Videos 1–3.

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Acknowledgements

This work was financially supported by the National Basic Research Program of China (No. 2017YFA0206702), the Natural Science Foundation of China (No. 21925110, 21890751, 91745113, U1832168, 21701164), the National Program for Support of Top-Notch Young Professionals, the Fundamental Research Funds for the Central Universities (No. WK 2060190084), the Anhui Provincial Natural Science Foundation (No. 1808085MB26) and the Strategic Priority Research Program of the Chinese Academy of Sciences (No. XDB36000000). H.L. was supported by the China Postdoctoral Science Foundation (No. 2018M642523). H.A.W. was supported by the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB22040402) and the National Natural Science Foundation of China (11525211). We thank X. Su of the Shanghai Synchrotron Radiation Facility for help with in situ XAS experiments, H. Yuan from G. Liu’s group at USTC for assistance with contact angle measurements and X. Zheng of the Hefei National Synchrotron Radiation Laboratory for help with XPS measurements.

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Author notes

  1. These authors contributed equally: Hongfei Liu, Jun Xia.

Authors and Affiliations

  1. Hefei National Laboratory for Physical Sciences at the Microscale, CAS Center for Excellence in Nanoscience, and CAS Key Laboratory of Mechanical Behavior and Design of Materials, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), University of Science and Technology of China, Hefei, P. R. China

    Hongfei Liu, Han Cheng, Wentuan Bi, Xiaolong Zu, Changzheng Wu & Yi Xie

  2. CAS Key Laboratory of Mechanical Behavior and Design of Materials, Department of Modern Mechanics, CAS Center for Excellence in Complex System Mechanics, University of Science and Technology of China, Hefei, China

    Jun Xia & HengAn Wu

  3. National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, P. R. China

    Nan Zhang & Wangsheng Chu

  4. Institute of Energy, Hefei Comprehensive National Science Center, Hefei, P. R. China

    Changzheng Wu & Yi Xie

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Contributions

C.W. and H.L. conceived the ideas, designed and carried out the experiments and co-wrote the manuscript. C.W. and Y.X. supervised the entire project and were responsible for the infrastructure and project direction. J.X. and H.W. conducted the ab initio molecular dynamic simulations of the Ga–Sn melting process. N.Z. and W.C. performed the XAS data analysis. H.L. and N.Z. performed the ab initio simulation of Sn K-edge XANES of liquid Ga–Sn alloy. H.C. and W.B. conducted part of the in situ XAS experiments and assisted with data analysis. X.Z. performed the in situ FT-IR spectroscopy experiments. All the authors participated in discussion of the results and manuscript preparation and revision.

Corresponding author

Correspondence to Changzheng Wu.

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Peer review information Nature Catalysis thanks Alessandro Longo 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 Methods, Figs. 1–33, Tables 1–5, Notes 1 and 2 and Refs. 1–41.

Supplementary Video 1

This video shows the affinity of the liquid Ga–Sn drop to the oxide-free copper plate.

Supplementary Video 2

This video records the melting process of solid Ga–Sn alloy during CO2 electroreduction at –0.96 V versus RHE. Magnetic stirring and CO2 bubbling were stopped to facilitate inspection of the Ga–Sn electrode. The electrolyte temperature was controlled by immersing the electrochemical cell in a hot water bath. This video shows no visual change of volume, shape or colour of the Ga–Sn alloy during the melting process, consistent with the maintained electrochemical active surface area (Supplementary Fig. 11) across the solid–liquid phase transition.

Supplementary Video 3

This video records the solidification process of liquid Ga–Sn alloy during CO2 electroreduction at –0.96 V versus RHE. The electrolyte temperature was controlled by immersing the electrochemical cell in an ice-water bath. This video indicates no visual change of volume, shape or colour of the Ga–Sn alloy during the solidification process.

Supplementary Data 1

The initial and final atomic coordinates of both the 2-Sn and 12-Sn Ga–Sn clusters for ab initio molecular dynamic simulations (Supplementary Fig. 26) are included in this file.

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Liu, H., Xia, J., Zhang, N. et al. Solid–liquid phase transition induced electrocatalytic switching from hydrogen evolution to highly selective CO2 reduction. Nat Catal 4, 202–211 (2021). https://doi.org/10.1038/s41929-021-00576-3

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