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Synthesis of noble metal chalcogenides via cation exchange reactions

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Abstract

Noble metal chalcogenides (NMCs) are an important class of materials with unique properties and widespread applications; however, the synthesis of these materials in a well-controlled manner remains challenging. Cation exchange (CE) transformation is a versatile, topotactic strategy which enables the synthesis of a range of materials, but its use for preparing NMCs has not been studied in detail, impeding the application of these materials. Here we demonstrate a robust and general strategy for the fabrication of a wide variety of NMCs via CE transformations, in which CuTe metal chalcogenides are used as sacrificial templates for CE with noble metal cations. The generality of the CE strategy is validated by the fabrication of NMCs with tailored morphologies (zero-dimension (0D), 1D, 2D and 3D), compositions (Pd/Pt/Rh/Ru/Ag/Au-based NMCs) and phases. In-depth mechanistic study shows that the well-controlled synthesis of NMCs is realized by kinetic control and solvent-dependent thermodynamic control.

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Fig. 1: The preparation of 2D NMCs via CE reactions.
Fig. 2: The influences of solvents on CE transformation.
Fig. 3: Theoretical simulations on CE transformation.
Fig. 4: Preparation of shaped Pd–Te tellurides.
Fig. 5: Preparation of Pd-based selenides and sulfides via CE transformation.

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Data availability

The additional characterization data, experimental data, and theoretical calculation data are provided in the Supplementary Information. Source data are provided with this paper.

Code availability

The computational codes used in this work are available from the commercial Vienna Ab initio Package and Accelrys Materials Studio.

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Acknowledgements

This work was financially supported by the Ministry of Science and Technology (2017YFA0208200, 2016YFA0204100), the National Natural Science Foundation of China (22025108, 51802206), the Natural Science Foundation of Jiangsu Province (BK20180846), the Guangdong Provincial Natural Science Fund for Distinguished Young Scholars (2021B1515020081), the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD), and start-up supports from Xiamen University and Guangzhou Key Laboratory of Low Dimensional Materials and Energy Storage Devices (20195010002).

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Author notes

  1. These authors contributed equally: Yonggang Feng, Yujin Ji.

Authors and Affiliations

  1. State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China

    Yonggang Feng, Ying Zhang & Xiaoqing Huang

  2. College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Jiangsu, China

    Yonggang Feng & Qi Shao

  3. Institute of Functional Nano & Soft Materials (FUNSOM), Soochow University, Jiangsu, China

    Yujin Ji & Youyong Li

  4. Guangzhou Key Laboratory of Low-Dimensional Materials and Energy Storage Devices, Collaborative Innovation Center of Advanced Energy Materials, School of Materials and Energy, Guangdong University of Technology, Guangzhou, China

    Yong Xu

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  1. Yonggang Feng
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Contributions

X.H. and Y.X. conceived and supervised the research. X.H., Y.X. and Y.F designed the experiments. X.H. and Y.F. performed most of the experiments and data analysis. X.H., Y.X., Y.F., Y.Z. and Q.S. participated in various aspects of the experiments and discussions. Y.J. and Y.L. performed the theoretical calculations. X.H., Y.X. and Y.F. wrote the paper. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Yong Xu or Xiaoqing Huang.

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Nature Synthesis thanks Humberto Gutierrez and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary handling editor: Peter Seavill, in collaboration with the Nature Synthesis team.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–44 and Tables 1–3.

Source data

Source Data Fig. 1

Raw data of XRD patterns for 2D tellurides and their corresponding references.

Source Data Fig. 2

Raw data of XRD patterns for the products obtained during cation exchange as well as plots of the elemental content in nanocrystals and solutions at different reaction times.

Source Data Fig. 3

Raw data of the relative energies during the Cu leaching and Pd introduction process. Raw data of the chemical potentials of Pd atoms in various solvents and plot of the binding energies compared to the charge of O in sulfoxide groups.

Source Data Fig. 5

Raw data of XRD patterns for 2D sulfides and their corresponding references.

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Feng, Y., Ji, Y., Zhang, Y. et al. Synthesis of noble metal chalcogenides via cation exchange reactions. Nat. Synth 1, 626–634 (2022). https://doi.org/10.1038/s44160-022-00117-1

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