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Abrading bulk metal into single atoms

Nature Nanotechnology volume 17, pages 403–407 (2022)Cite this article

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Abstract

Single-atom catalysts have recently attracted considerable attention because of their highly efficient metal utilization and unique properties. Finding a green, facile method to synthesize them is key to their widespread commercialization. Here we show that single-atom catalysts (including iron, cobalt, nickel and copper) can be prepared via a top-down abrasion method, in which the bulk metal is directly atomized onto different supports, such as carbon frameworks, oxides and nitrides. The level of metal loading can be easily tuned by changing the abrasion rate. No synthetic chemicals, solvents or even water were used in the process and no by-products or waste were generated. The underlying reaction mechanism involves the mechanochemical force in situ generating defects on the supports, then trapping and stably sequestering atomized metals.

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Fig. 1: Schematic comparing the different methods for preparing SACs.
Fig. 2: Characterizations of single-atom metal–N–C.
Fig. 3: Theoretical analysis.
Fig. 4: Extension to different supports.

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Data availability

The data that support the findings of this study are presented in the main text and the Supplementary Information, and are available from the corresponding authors upon reasonable request.

References

  1. Liu, L. & Corma, A. Metal catalysts for heterogeneous catalysis: from single atoms to nanoclusters and nanoparticles. Chem. Rev. 118, 4981–5079 (2018).

    Article  CAS  Google Scholar 

  2. Cui, X., Li, W., Ryabchuk, P., Junge, K. & Beller, M. Bridging homogeneous and heterogeneous catalysis by heterogeneous single-metal-site catalysts. Nat. Catal. 1, 385–397 (2018).

    Article  CAS  Google Scholar 

  3. Beniya, A. & Higashi, S. Towards dense single-atom catalysts for future automotive applications. Nat. Catal. 2, 590–602 (2019).

    Article  Google Scholar 

  4. Wang, A., Li, J. & Zhang, T. Heterogeneous single-atom catalysis. Nat. Rev. Chem. 2, 65–81 (2018).

    Article  CAS  Google Scholar 

  5. Therrien, A. J. et al. An atomic-scale view of single-site Pt catalysis for low-temperature CO oxidation. Nat. Catal. 1, 192–198 (2018).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  7. 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 

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

    Article  CAS  Google Scholar 

  9. Li, H. et al. Synergetic interaction between neighbouring platinum monomers in CO2 hydrogenation. Nat. Nanotechnol. 13, 411–417 (2018).

    Article  CAS  Google Scholar 

  10. Yao, Y. et al. High temperature shockwave stabilized single atoms. Nat. Nanotechnol. 14, 851–857 (2019).

    Article  CAS  Google Scholar 

  11. Malta, G. et al. Identification of single-site gold catalysis in acetylene hydrochlorination. Science 355, 1399–1403 (2017).

    Article  CAS  Google Scholar 

  12. 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 

  13. Gu, J., Hsu, C. S., Bai, L., Chen, H. M. & Hu, X. Atomically dispersed Fe3+ sites catalyze efficient CO2 electroreduction to CO. Science 364, 1091–1094 (2019).

    Article  CAS  Google Scholar 

  14. Zhang, J. et al. Single platinum atoms immobilized on an MXene as an efficient catalyst for the hydrogen evolution reaction. Nat. Catal. 1, 985–992 (2018).

    Article  CAS  Google Scholar 

  15. Liu, D. et al. Atomically dispersed platinum supported on curved carbon supports for efficient electrocatalytic hydrogen evolution. Nat. Energy 4, 512–518 (2019).

    Article  CAS  Google Scholar 

  16. Cao, L. et al. Identification of single-atom active sites in carbon-based cobalt catalysts during electrocatalytic hydrogen evolution. Nat. Catal. 2, 134–141 (2019).

    Article  CAS  Google Scholar 

  17. Guan, J. et al. Water oxidation on a mononuclear manganese heterogeneous catalyst. Nat. Catal. 1, 870–877 (2018).

    Article  CAS  Google Scholar 

  18. He, X. et al. Mechanochemical kilogram-scale synthesis of noble metal single-atom catalysts. Cell Rep. Phys. Sci. 1, 100004 (2020).

    Article  Google Scholar 

  19. Jin, H. et al. Simple and scalable mechanochemical synthesis of noble metal catalysts with single atoms toward highly efficient hydrogen evolution. Adv. Funct. Mater. 30, 2000531 (2020).

    Article  CAS  Google Scholar 

  20. Gan, T. et al. Unveiling the kilogram-scale gold single-atom catalysts via ball milling for preferential oxidation of CO in excess hydrogen. Chem. Eng. J. 389, 124490 (2020).

    Article  CAS  Google Scholar 

  21. Gan, T. et al. Facile synthesis of kilogram-scale co-alloyed Pt single-atom catalysts via ball milling for hydrodeoxygenation of 5-hydroxymethylfurfural. ACS Sustain. Chem. Eng. 8, 8692–8699 (2020).

    Article  CAS  Google Scholar 

  22. Wei, S. et al. Direct observation of noble metal nanoparticles transforming to thermally stable single atoms. Nat. Nanotechnol. 13, 856–861 (2018).

    Article  CAS  Google Scholar 

  23. Goodman, E. D. et al. Catalyst deactivation via decomposition into single atoms and the role of metal loading. Nat. Catal. 2, 748–755 (2019).

    Article  CAS  Google Scholar 

  24. Qu, Y. et al. Direct transformation of bulk copper into copper single sites via emitting and trapping of atoms. Nat. Catal. 1, 781–786 (2018).

    Article  CAS  Google Scholar 

  25. Han, G. F. et al. Dissociating stable nitrogen molecules under mild conditions by cyclic strain engineering. Sci. Adv. 5, eaax8275 (2019).

    Article  CAS  Google Scholar 

  26. Wan, X. et al. Fe–N–C electrocatalyst with dense active sites and efficient mass transport for high-performance proton exchange membrane fuel cells. Nat. Catal. 2, 259–268 (2019).

    Article  CAS  Google Scholar 

  27. Zitolo, A. et al. Identification of catalytic sites for oxygen reduction in iron- and nitrogen-doped graphene materials. Nat. Mater. 14, 937–942 (2015).

    Article  CAS  Google Scholar 

  28. Li, J. et al. Atomically dispersed manganese catalysts for oxygen reduction in proton-exchange membrane fuel cells. Nat. Catal. 1, 935–945 (2018).

    Article  CAS  Google Scholar 

  29. Kramm, U. I., Lefèvre, M., Larouche, N., Schmeisser, D. & Dodelet, J. Correlations between mass activity and physicochemical properties of Fe/N/C catalysts for the ORR in PEM fuel cell via 57Fe Mössbauer spectroscopy and other techniques. J. Am. Chem. Soc. 136, 978–985 (2014).

    Article  CAS  Google Scholar 

  30. Fei, H. et al. General synthesis and definitive structural identification of MN4C4 single-atom catalysts with tunable electrocatalytic activities. Nat. Catal. 1, 63–72 (2018).

    Article  CAS  Google Scholar 

  31. Tong, W. P., Tao, N. R., Wang, Z. B., Lu, J. & Lu, K. Nitriding iron at lower temperatures. Science 299, 686–688 (2003).

    Article  CAS  Google Scholar 

  32. Cretu, O. et al. Migration and localization of metal atoms on strained graphene. Phys. Rev. Lett. 105, 196102 (2010).

    Article  Google Scholar 

  33. Robertson, A. W. et al. Dynamics of single Fe atoms in graphene vacancies. Nano Lett. 13, 1468–1475 (2013).

    Article  CAS  Google Scholar 

  34. Ravel, B. & Newville, M. ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT. J. Synchrotron Radiat. 12, 537–541 (2005).

    Article  CAS  Google Scholar 

  35. Clark, S. J. et al. First principles methods using CASTEP. Z. Kristallogr. Cryst. Mater. 220, 567–570 (2005).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

We thank M. Chhowalla for help and discussion. We are grateful for the use of the Pohang Accelerator Laboratory (6D UNIST-PAL beamline, South Korea). J.-B.B. acknowledges support from the Creative Research Initiative (CRI, 2014R1A3A2069102) and Science Research Center (SRC, 2016R1A5A1009405) programmes through the National Research Foundation (NRF) of Korea. J.-B.B also acknowledges the U-K Brand Project (1.200096.01) of UNIST. H.Y.J. acknowledges support from the National R&D Program (2020M3F3A2A01082618) through the National Research Foundation (NRF) of Korea. F.L. acknowledges financial support from Fudan University (JIH2203011). Funding for J.W., A.I.R., W.Z. and R.G. was provided by the International Partnership Program of the Chinese Academy of Sciences (121421KYSB20170020) and the State Key Laboratory of Catalysis in Dalian Institute of Chemical Physics (N-16-07). Z.A. acknowledges financial support (221777033) from the National Natural Science Foundation of China.

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Authors and Affiliations

  1. School of Energy and Chemical Engineering/Center for Dimension-Controllable Organic Frameworks, Ulsan National Institute of Science and Technology (UNIST), Ulsan, South Korea

    Gao-Feng Han, Feng Li, Yoon-Kwang Im, Soo-Young Yu, Jong-Pil Jeon, Seok-Jin Kim & Jong-Beom Baek

  2. Laboratory of Advanced Materials, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, P. R. China

    Feng Li

  3. Mössbauer Effect Data Center, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, P. R. China

    Alexandre I. Rykov, Wenhui Zhou, Rile Ge & Junhu Wang

  4. Institute of Environmental Health and Pollution Control, School of Environmental Science and Engineering, Guangdong University of Technology, Guangzhou, P. R. China

    Zhimin Ao

  5. Graduate School of Semiconductor Materials and Devices Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan, South Korea

    Tae Joo Shin & Hu Young Jeong

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  1. Gao-Feng Han
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Contributions

J.-B.B. conceived the project and oversaw all the research phases. J.-B.B. and G.-F.H. designed the project. G.-F.H. carried out the sample synthesis and structural characterization. F.L. and Z.A. performed the DFT calculation. T.J.S., Y.-K.I., J.-P.J. and S.-J.K. assisted with the XAS study. H.Y.J. conducted the HAADF-STEM measurements. J.W., A.I.R., W.Z. and R.G. measured and interpreted the Mössbauer spectroscopy. S.-Y.Y. designed the scheme. Data collection and analysis were conducted by J.-B.B., G.-F.H. and F.L. All the authors contributed to the writing of the manuscript.

Corresponding authors

Correspondence to Feng Li, Hu Young Jeong or Jong-Beom Baek.

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Nature Nanotechnology thanks the anonymous reviewers for their contribution to the peer review of this work.

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Supplementary methods, notes, Figs. 1–15 and Tables 1–5.

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Han, GF., Li, F., Rykov, A.I. et al. Abrading bulk metal into single atoms. Nat. Nanotechnol. 17, 403–407 (2022). https://doi.org/10.1038/s41565-022-01075-7

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