Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Direct transformation of bulk copper into copper single sites via emitting and trapping of atoms

Nature Catalysis volume 1, pages 781–786 (2018)Cite this article

Subjects

Abstract

Single-atom catalysts exhibit intriguing properties and receive widespread interest for their effectiveness in promoting a variety of catalytic reactions, making them highly desired motifs in materials science. However, common approaches to the synthesis of these materials often require tedious procedures and lack appropriate interactions between the metal atoms and supports. Here, we report a simple and practical strategy to access the large-scale synthesis of single-atom catalysts via direct atoms emitting from bulk metals, and the subsequent trapping on nitrogen-rich porous carbon with the assistance of ammonia. First, the ammonia coordinates with the copper atoms to form volatile Cu(NH3)x species based on the strong Lewis acid–base interaction. Then, following transportation under an ammonia atmosphere, the Cu(NH3)x species are trapped by the defects on the nitrogen-rich carbon support, forming the isolated copper sites. This strategy is readily scalable and has been confirmed as feasible for producing functional single-atom catalysts at industrial levels.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Schematic of the preparation of Cu-SAs/N-C.
Fig. 2: Characterization of copper SACs and pyrolysed ZIF-8.
Fig. 3: Chemical state and coordination information for copper SACs.
Fig. 4: ORR activity of Cu-SAs/N-C and its large-scale production.
Fig. 5: Characterization of Ni/Co-SAs/N-C.

Similar content being viewed by others

Data availability

The main data supporting the findings of this study are available within the article and its Supplementary Information. Extra data are available from the corresponding authors upon request.

References

  1. Boronat, M. et al. Theoretical and experimental insights into the origin of the catalytic activity of subnanometric gold clusters: attempts to predict reactivity with clusters and nanoparticles of gold. Acc. Chem. Res. 47, 834–844 (2013).

    Article  Google Scholar 

  2. Wei, H. et al. FeOx-supported platinum single-atom and pseudo-single-atom catalysts for chemoselective hydrogenation of functionalized nitroarenes. Nat. Commun. 5, 5634 (2014).

    Article  CAS  Google Scholar 

  3. Yan, H. et al. Single-atom Pd1/graphene catalyst achieved by atomic layer deposition: remarkable performance in selective hydrogenation of 1,3-butadiene. J. Am. Chem. Soc. 137, 10484–10487 (2015).

    Article  CAS  Google Scholar 

  4. Nie, L. et al. Activation of surface lattice oxygen in single-atom Pt/CeO2 for low-temperature CO oxidation. Science 358, 1419–1423 (2017).

    Article  CAS  Google Scholar 

  5. Qiao, B. et al. Single-atom catalysis of CO oxidation using Pt1/FeOx. Nat. Chem. 3, 634–641 (2011).

    Article  CAS  Google Scholar 

  6. Kwon, Y. et al. Selective activation of methane on single-atom catalyst of rhodium dispersed on zirconia for direct conversion. J. Am. Chem. Soc. 139, 17694–17699 (2017).

    Article  CAS  Google Scholar 

  7. Guo, X. et al. Direct, nonoxidative conversion of methane to ethylene, aromatics, and hydrogen. Science 344, 616–619 (2014).

    Article  CAS  Google Scholar 

  8. Yin, P. et al. Single cobalt atoms with precise N-coordination as superior oxygen reduction reaction catalysts. Angew. Chem. Int. Ed. 55, 10800–10805 (2016).

    Article  CAS  Google Scholar 

  9. Chung, H. T. et al. Direct atomic-level insight into the active sites of a high-performance PGM-free ORR catalyst. Science 357, 479–484 (2017).

    Article  CAS  Google Scholar 

  10. Chen, P. et al. Atomically dispersed iron–nitrogen species as electrocatalysts for bifunctional oxygen evolution and reduction reactions. Angew. Chem. Int. Ed. 56, 610–614 (2017).

    Article  CAS  Google Scholar 

  11. Zheng, Y. et al. Molecule-level g-C3N4 coordinated transition metals as a new class of electrocatalysts for oxygen electrode reactions. J. Am. Chem. Soc. 139, 3336–3339 (2017).

    Article  CAS  Google Scholar 

  12. Zhang, L. et al. Efficient and durable Au alloyed Pd single-atom catalyst for the Ullmann reaction of aryl chlorides in water. ACS Catal. 4, 1546–1553 (2014).

    Article  CAS  Google Scholar 

  13. Zhang, X. et al. Catalytically active single-atom niobium in graphitic layers. Nat. Commun. 4, 1924 (2013).

    Article  Google Scholar 

  14. Jiao, Y. et al. Molecular scaffolding strategy with synergistic active centers to facilitate electrocatalytic CO2 reduction to hydrocarbon/alcohol. J. Am. Chem. Soc. 139, 18093–18100 (2017).

    Article  CAS  Google Scholar 

  15. Zhang, L., Han, L., Liu, H., Liu, X. & Luo, J. Potential-cycling synthesis of single platinum atoms for efficient hydrogen evolution in neutral media. Angew. Chem. Int. Ed. 56, 13694–13698 (2017).

    Article  CAS  Google Scholar 

  16. Long, R. et al. Isolation of Cu atoms in Pd lattice: forming highly selective sites for photocatalytic conversion of CO2 to CH4. J. Am. Chem. Soc. 139, 4486–4492 (2017).

    Article  CAS  Google Scholar 

  17. Abbet, S. et al. Acetylene cyclotrimerization on supported size-selected Pdn clusters (1 ≤ n ≤ 30): one atom is enough! J. Am. Chem. Soc. 122, 3453–3457 (2000).

    Article  CAS  Google Scholar 

  18. Peters, A. W. et al. Atomically precise growth of catalytically active cobalt sulfide on flat surfaces and within a metal-organic framework via atomic layer deposition. ACS Nano 9, 8484–8490 (2015).

    Article  CAS  Google Scholar 

  19. Lin, J. et al. Remarkable performance of Ir1/FeOx single-atom catalyst in water gas shift reaction. J. Am. Chem. Soc. 135, 15314–15317 (2013).

    Article  CAS  Google Scholar 

  20. Lin, L. et al. Low-temperature hydrogen production from water and methanol using Pt/α-MoC catalysts. Nature 544, 80–83 (2017).

    Article  CAS  Google Scholar 

  21. Liu, P. et al. Photochemical route for synthesizing atomically dispersed palladium catalysts. Science 352, 797–800 (2016).

    Article  CAS  Google Scholar 

  22. Jones, J. et al. Thermally stable single-atom platinum-on-ceria catalysts via atom trapping. Science 353, 150–154 (2016).

    Article  CAS  Google Scholar 

  23. Chen, S. et al. Three-dimensional N-doped graphene hydrogel/NiCo double hydroxide electrocatalysts for highly efficient oxygen evolution. Angew. Chem. Int. Ed. 52, 13567–13570 (2013).

    Article  CAS  Google Scholar 

  24. Qu, L. et al. Nitrogen-doped graphene as efficient metal-free electrocatalyst for oxygen reduction in fuel cells. ACS Nano 4, 1321–1326 (2010).

    Article  CAS  Google Scholar 

  25. Gong, J. et al. Synthesis of ethanol via syngas on Cu/SiO2 catalysts with balanced Cu0–Cu+ sites. J. Am. Chem. Soc. 134, 13922–13925 (2012).

    Article  CAS  Google Scholar 

  26. Wang, J. et al. Design of N-coordinated dual-metal sites: a stable and active Pt-free catalyst for acidic oxygen reduction reaction. J. Am. Chem. Soc. 139, 17281–17284 (2017).

    Article  CAS  Google Scholar 

  27. Nesselberger, M. et al. The particle size effect on the oxygen reduction reaction activity of Pt catalysts: influence of electrolyte and relation to single crystal models. J. Am. Chem. Soc. 133, 17428–17433 (2011).

    Article  CAS  Google Scholar 

  28. Suntivich, J. et al. Electrocatalytic measurement methodology of oxide catalysts using a thin-film rotating disk electrode. J. Electrochem. Soc. 157, B1263–B1268 (2010).

    Article  CAS  Google Scholar 

  29. Piana, M., Catanorchi, S. & Gasteiger, H. Kinetics of non-platinum group metal catalysts for the oxygen reduction reaction in alkaline medium. ECS Trans. 16, 2045–2055 (2008).

    Article  CAS  Google Scholar 

  30. Lu, Y. et al. Strongly coupled Pd nanotetrahedron/tungsten oxide nanosheet hybrids with enhanced catalytic activity and stability as oxygen reduction electrocatalysts. J. Am. Chem. Soc. 136, 11687–11697 (2014).

    Article  CAS  Google Scholar 

  31. Choi, C. et al. Unraveling the nature of sites active toward hydrogen peroxide reduction in Fe–N–C catalysts. Angew. Chem. Int. Ed. 129, 8935–8938 (2017).

    Article  Google Scholar 

  32. Zeradjanin, A. et al. Frequent pitfalls in the characterization of electrodes designed for electrochemical energy conversion and storage. ChemSusChem. 11, 1278–1284 (2018).

    Article  CAS  Google Scholar 

  33. Ramaswamy, N. & Mukerjee, S. Fundamental mechanistic understanding of electrocatalysis of oxygen reduction on Pt and non-Pt surfaces: acid versus alkaline media. Adv. Phys. Chem. 2012, 491604 (2012).

    Article  Google Scholar 

  34. Ramaswamy, N. et al. Activity descriptor identification for oxygen reduction on nonprecious electrocatalysts: linking surface science to coordination chemistry. J. Am. Chem. Soc. 135, 15443–15449 (2013).

    Article  CAS  Google Scholar 

  35. Liang, Y. et al. Co3O4 nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction. Nat. Mater. 10, 780–786 (2011).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Key R&D Program of China 2017YFA (0208300) and National Natural Science Foundation of China (21522107, 21671180, 21521091, 21390393 and U1463202). We thank the photoemission endstations beamline 1W1B station in the Beijing Synchrotron Radiation Facility (BSRF), BL14W1 at the Shanghai Synchrotron Radiation Facility and BL10B and BL11U at the National Synchrotron Radiation Laboratory for help with the characterizations.

Author information

Authors and Affiliations

  1. Department of Chemistry, iChEM, University of Science and Technology of China, Hefei, China

    Yunteng Qu, Zhijun Li, Zhengkun Yang, Changming Zhao, Jing Wang, Chao Zhao, Xin Wang, Fangyao Zhou & Yuen Wu

  2. Department of Chemistry, Tsinghua University, Beijing, China

    Wenxing Chen & Yadong Li

  3. Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, China

    Yue Lin

  4. New Energy and Sensing Technology Lab, Department of Chemistry, College of Science, Shanghai University, Shanghai, China

    Tongwei Yuan

  5. Beijing Advanced Innovation Center for Soft Matter Science and Engineering and State Key Lab of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing, China

    Zhongbin Zhuang

Authors
  1. Yunteng Qu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Zhijun Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Wenxing Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Yue Lin
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Tongwei Yuan
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Zhengkun Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Changming Zhao
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Jing Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Chao Zhao
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Xin Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Fangyao Zhou
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Zhongbin Zhuang
    View author publications

    You can also search for this author in PubMed Google Scholar

  13. Yuen Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

  14. Yadong Li
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

Y.Li and Y.W. conceived the idea and co-wrote the paper. Y.Q. carried out the sample synthesis, characterization and ORR measurement. Z.L., Z.Z., Z.Y., C.Z., T.Y., X.W., F.Z., C.Z. and J.W. helped with the modification of the paper. W.C. helped with the XAFS measurements and discussion. Y.Lin helped with the spherical aberration electron microscopy tests and discussion. All authors contributed to the overall scientific interpretation and edited the manuscript.

Corresponding authors

Correspondence to Yuen Wu or Yadong Li.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary Figures 1–27 & Supplementary Tables 1–3

Supplementary Movie

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Qu, Y., Li, Z., Chen, W. et al. Direct transformation of bulk copper into copper single sites via emitting and trapping of atoms. Nat Catal 1, 781–786 (2018). https://doi.org/10.1038/s41929-018-0146-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41929-018-0146-x

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing