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Robust Anion Exchange Realized in Crystalline Metal Cyanamide Nanoparticles

  • Bingquan Jia
    Bingquan Jia
    State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, P. R. China
    Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, P. R. China
    More by Bingquan Jia
  • Wei Zhao
    Wei Zhao
    Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, P. R. China
    More by Wei Zhao
  • Du Sun*
    Du Sun
    State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, P. R. China
    Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, P. R. China
    *E-mail: [email protected] (D.S.).
    More by Du Sun
  • Linggang Fan
    Linggang Fan
    State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, P. R. China
    Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, P. R. China
    More by Linggang Fan
  • Heliang Yao
    Heliang Yao
    State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, P. R. China
    Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, P. R. China
    More by Heliang Yao
  • Ping Lu
    Ping Lu
    State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, P. R. China
    Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, P. R. China
    More by Ping Lu
  • FangFang Xu*
    FangFang Xu
    State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, P. R. China
    Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, P. R. China
    *E-mail: [email protected] (F.X.).
    More by FangFang Xu
  • , and 
  • Fuqiang Huang*
    Fuqiang Huang
    State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, P. R. China
    Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, P. R. China
    Beijing National Laboratory for Molecular Sciences and State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China
    *E-mail: [email protected] (F.H.).
Cite this: Chem. Mater. 2019, 31, 22, 9532–9539
Publication Date (Web):November 6, 2019
https://doi.org/10.1021/acs.chemmater.9b03934
Copyright © 2019 American Chemical Society
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Abstract

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Solution-mediated sequential ion exchange has emerged as a powerful yet simple technique to transform nanoparticulates into a complex architecture. However, the state-of-the-art demonstration of such fine-tailored nanostructures greatly relied on cation exchange reaction because it remains to be a great challenge to apply anion exchange without interfering the original morphology and crystallinity of the target particles. Herein, metal cyanamides with a looser cation sublattice enabled by the quasi-linear [NCN]2– anion units are discovered to be ideal parent compounds to accomplish robust anion exchange reactions. The complete conversion from metal cyanamide nanoparticles to metal chalcogenide nanoparticles (CdNCN to CdS, CdNCN to CdSe, and MnNCN to MnS) is successfully realized by low-temperature reaction in colloidal solution. The nanoparticles retain both the morphology and crystallinity throughout the entire exchange process. In-depth study reveals that the structural similarity in cation packing facilitates the exchange process, and such behavior is independent of the material composition. The quasi-linear structure of the three-atom [NCN]2– anion results in anisotropic lattice spaciousness, which helps bypass the diffusion rate discrepancy and lattice framework collapse commonly encountered in compounds consisting of single-atom anions. This work sheds light on extending the ion exchange reactions as a synthetic toolbox to a much broader library in nanoparticle synthesis.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.chemmater.9b03934.

  • Absorption, PL and IR spectra; distribution data; and XRD, HRTEM and HAADF data (PDF)

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