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.

Synthesis of core/shell nanocrystals with ordered intermetallic single-atom alloy layers for nitrate electroreduction to ammonia

Nature Synthesis (2023)Cite this article

Subjects

A Publisher Correction to this article was published on 22 March 2023

This article has been updated

Abstract

Structurally ordered intermetallic nanocrystals (NCs) and single-atom catalysts (SACs) are two emerging catalytic motifs for sustainable chemical production and energy conversion. However, both have synthetic limitations which can lead to the aggregation of NCs or metal atoms. Single-atom alloys (SAAs), which contain isolated metal atoms in a host metal, can overcome the aggregation concern because of the thermodynamic stabilization of single atoms on host metal surfaces. Here we report a direct solution-phase synthesis of Cu/CuAu core/shell NCs with tunable SAA layers. This synthesis can be extended to other Cu/CuM (M = Pt, Pd) systems, in which M atoms are isolated in the copper host. Using this method, the density of SAAs on a copper surface can be controlled, resulting in both low and high densities of single atoms. Alloying gold into the copper matrix introduced ligand effects that optimized the chemisorption of *NO3 and *N. As a result, the densely packed Cu/CuAu material demonstrated a high selectivity toward NH3 from the electrocatalytic nitrate reduction reaction with an 85.5% Faradaic efficiency while maintaining a high yield rate of 8.47 mol h−1 g−1. This work advances the design of atomically precise catalytic sites by creating core/shell NCs with SAA atomic layers, opening an avenue for broad catalytic applications.

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

Access options

Rent or buy this article

Get just this article for as long as you need it

$39.95

Learn more

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

Fig. 1: Schematic illustration of the core/shell Cu/CuAu SAA synthesis.
Fig. 2: Characterizations of core/shell Cu/CuAu SAA nanocubes.
Fig. 3: Structural characterizations of the Cu/CuAu SAA nanocubes.
Fig. 4: NO3RR performance of the Cu/CuAu ordered SAA nanocubes.
Fig. 5: NO3RR reaction pathway and activity map.

Data availability

The data supporting the finding of the study are available in the paper and its Supplementary Information. Source data are provided with this paper.

Change history

References

  1. van der Hoeven, J. E. S. et al. Unlocking synergy in bimetallic catalysts by core–shell design. Nat. Mater. 20, 1216–1220 (2021).

    Article  PubMed  Google Scholar 

  2. Wu, P. et al. Harnessing strong metal–support interactions via a reverse route. Nat. Commun. 11, 3042 (2020).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  3. Gawande, M. B. et al. Core–shell nanoparticles: synthesis and applications in catalysis and electrocatalysis. Chem. Soc. Rev. 44, 7540–7590 (2015).

    Article  CAS  PubMed  Google Scholar 

  4. Zhao, X. & Sasaki, K. Advanced Pt-based core–shell electrocatalysts for fuel cell cathodes. Acc. Chem. Res. 55, 1226–1236 (2022).

    Article  CAS  PubMed  Google Scholar 

  5. Yang, X. et al. Modulating electronic structure of an Au-nanorod-core–PdPt-alloy-shell catalyst for efficient alcohol electro-oxidation. Adv. Energy Mater. 11, 2100812 (2021).

    Article  CAS  Google Scholar 

  6. Wang, X. et al. Palladium–platinum core–shell icosahedra with substantially enhanced activity and durability towards oxygen reduction. Nat. Commun. 6, 7594 (2015).

    Article  PubMed  Google Scholar 

  7. Wang, H. et al. Significantly enhanced overall water splitting performance by partial oxidation of Ir through Au modification in core–shell alloy structure. J. Am. Chem. Soc. 143, 4639–4645 (2021).

    Article  CAS  PubMed  Google Scholar 

  8. Li, M. et al. Exclusive strain effect boosts overall water splitting in PdCu/Ir core/shell nanocrystals. Angew. Chem. Int. Ed. 60, 8243–8250 (2021).

    Article  CAS  Google Scholar 

  9. Zhuang, T.-T. et al. Steering post-C–C coupling selectivity enables high efficiency electroreduction of carbon dioxide to multi-carbon alcohols. Nat. Catal. 1, 421–428 (2018).

    Article  CAS  Google Scholar 

  10. Luc, W. et al. Ag–Sn bimetallic catalyst with a core–shell structure for CO2 reduction. J. Am. Chem. Soc. 139, 1885–1893 (2017).

    Article  CAS  PubMed  Google Scholar 

  11. Liu, C. et al. Favorable core/shell interface within Co2P/Pt nanorods for oxygen reduction electrocatalysis. Nano Lett. 18, 7870–7875 (2018).

    Article  CAS  PubMed  Google Scholar 

  12. Zhang, S. et al. Monodisperse core/shell Ni/FePt nanoparticles and their conversion to Ni/Pt to catalyze oxygen reduction. J. Am. Chem. Soc. 136, 15921–15924 (2014).

    Article  CAS  PubMed  Google Scholar 

  13. Ji, Y. et al. Selective CO-to-acetate electroreduction via intermediate adsorption tuning on ordered Cu–Pd sites. Nat. Catal. 5, 251–258 (2022).

  14. Yang, C.-L. et al. Sulfur-anchoring synthesis of platinum intermetallic nanoparticle catalysts for fuel cells. Science 374, 459–464 (2021).

    Article  CAS  PubMed  Google Scholar 

  15. Wang, D. et al. Structurally ordered intermetallic platinum–cobalt core–shell nanoparticles with enhanced activity and stability as oxygen reduction electrocatalysts. Nat. Mater. 12, 81–87 (2013).

    Article  CAS  PubMed  Google Scholar 

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

    Article  CAS  Google Scholar 

  17. Yang, X.-F. et al. Single-atom catalysts: a new frontier in heterogeneous catalysis. Acc. Chem. Res. 46, 1740–1748 (2013).

    Article  CAS  PubMed  Google Scholar 

  18. Liu, J.-C., Xiao, H. & Li, J. Constructing high-loading single-atom/cluster catalysts via an electrochemical potential window strategy. J. Am. Chem. Soc. 142, 3375–3383 (2020).

    Article  CAS  PubMed  Google Scholar 

  19. Chen, Y. et al. Single-atom catalysts: synthetic strategies and electrochemical applications. Joule 2, 1242–1264 (2018).

    Article  CAS  Google Scholar 

  20. Zhang, T., Walsh, A. G., Yu, J. & Zhang, P. Single-atom alloy catalysts: structural analysis, electronic properties and catalytic activities. Chem. Soc. Rev. 50, 569–588 (2021).

    Article  CAS  PubMed  Google Scholar 

  21. Kaiser, S. K., Chen, Z., Faust Akl, D., Mitchell, S. & Pérez-Ramírez, J. Single-atom catalysts across the periodic table. Chem. Rev. 120, 11703–11809 (2020).

    Article  CAS  PubMed  Google Scholar 

  22. Hannagan, R. T., Giannakakis, G., Flytzani-Stephanopoulos, M. & Sykes, E. C. H. Single-atom alloy catalysis. Chem. Rev. 120, 12044–12088 (2020).

    Article  CAS  PubMed  Google Scholar 

  23. Han, A. et al. Isolating contiguous Pt atoms and forming Pt–Zn intermetallic nanoparticles to regulate selectivity in 4-nitrophenylacetylene hydrogenation. Nat. Commun. 10, 3787 (2019).

    Article  PubMed  PubMed Central  Google Scholar 

  24. Feng, Q. et al. Isolated single-atom Pd sites in intermetallic nanostructures: high catalytic selectivity for semihydrogenation of alkynes. J. Am. Chem. Soc. 139, 7294–7301 (2017).

    Article  CAS  PubMed  Google Scholar 

  25. Armbrüster, M. et al. Al13Fe4 as a low-cost alternative for palladium in heterogeneous hydrogenation. Nat. Mater. 11, 690–693 (2012).

    Article  PubMed  Google Scholar 

  26. Nakaya, Y., Hirayama, J., Yamazoe, S., Shimizu, K.-I. & Furukawa, S. Single-atom Pt in intermetallics as an ultrastable and selective catalyst for propane dehydrogenation. Nat. Commun. 11, 2838 (2020).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  27. Xia, X. H., Wang, Y., Ruditskiy, A. & Xia, Y. N. 25th anniversary article: galvanic replacement: a simple and versatile route to hollow nanostructures with tunable and well-controlled properties. Adv. Mater. 25, 6313–6333 (2013).

    Article  CAS  PubMed  Google Scholar 

  28. González, E., Arbiol, J. & Puntes, V. F. Carving at the nanoscale: sequential galvanic exchange and kirkendall growth at room temperature. Science 334, 1377–1380 (2011).

    Article  PubMed  Google Scholar 

  29. Chen, F.-Y. et al. Efficient conversion of low-concentration nitrate sources into ammonia on a Ru-dispersed Cu nanowire electrocatalyst. Nat. Nanotechnol. 17, 759–767 (2022).

    Article  CAS  PubMed  Google Scholar 

  30. Wang, Y., Wang, C., Li, M., Yu, Y. & Zhang, B. Nitrate electroreduction: mechanism insight, in situ characterization, performance evaluation, and challenges. Chem. Soc. Rev. 50, 6720–6733 (2021).

    Article  CAS  PubMed  Google Scholar 

  31. Min, B. et al. Powering the remediation of the nitrogen cycle: progress and perspectives of electrochemical nitrate reduction. Ind. Eng. Chem. Res. 60, 14635–14650 (2021).

    Article  CAS  Google Scholar 

  32. Rosca, V., Duca, M., de Groot, M. T. & Koper, M. T. M. Nitrogen cycle electrocatalysis. Chem. Rev. 109, 2209–2244 (2009).

    Article  CAS  PubMed  Google Scholar 

  33. Guo, H. et al. Shape-selective formation of monodisperse copper nanospheres and nanocubes via disproportionation reaction route and their optical properties. J. Phys. Chem. C 118, 9801–9808 (2014).

    Article  CAS  Google Scholar 

  34. Zhao, J., Chen, B. & Wang, F. Shedding light on the role of misfit strain in controlling core–shell nanocrystals. Adv. Mater. 32, 2004142 (2020).

    Article  CAS  Google Scholar 

  35. Kim, D. et al. Electrochemical activation of CO2 through atomic ordering transformations of AuCu nanoparticles. J. Am. Chem. Soc. 139, 8329–8336 (2017).

    Article  CAS  PubMed  Google Scholar 

  36. Wan, J. et al. Defect effects on TiO2 nanosheets: stabilizing single atomic site au and promoting catalytic properties. Adv. Mater. 30, 1705369 (2018).

    Article  Google Scholar 

  37. Gao, Q. et al. Breaking adsorption-energy scaling limitations of electrocatalytic nitrate reduction on intermetallic CuPd nanocubes by machine-learned insights. Nat. Commun. 13, 2338 (2022).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  38. Wu, Z.-Y. et al. Electrochemical ammonia synthesis via nitrate reduction on Fe single atom catalyst. Nat. Commun. 12, 2870 (2021).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  39. Wang, Y., Zhou, W., Jia, R., Yu, Y. & Zhang, B. Unveiling the activity origin of a copper-based electrocatalyst for selective nitrate reduction to ammonia. Angew. Chem. Int. Ed. 59, 5350–5354 (2020).

    Article  CAS  Google Scholar 

  40. Wang, Y. et al. Enhanced nitrate-to-ammonia activity on copper-nickel alloys via tuning of intermediate adsorption. J. Am. Chem. Soc. 142, 5702–5708 (2020).

    Article  CAS  PubMed  Google Scholar 

  41. Li, J. et al. Efficient ammonia electrosynthesis from nitrate on strained ruthenium nanoclusters. J. Am. Chem. Soc. 142, 7036–7046 (2020).

    Article  CAS  PubMed  Google Scholar 

  42. Yao, Y., Zhu, S., Wang, H., Li, H. & Shao, M. A spectroscopic study on the nitrogen electrochemical reduction reaction on gold and platinum surfaces. J. Am. Chem. Soc. 140, 1496–1501 (2018).

    Article  CAS  PubMed  Google Scholar 

  43. da Cunha, M. C. P. M., De Souza, J. P. I. & Nart, F. C. Reaction pathways for reduction of nitrate ions on platinum, rhodium, and platinum–rhodium alloy electrodes. Langmuir 16, 771–777 (2000).

    Article  Google Scholar 

  44. Yao, Y., Zhu, S., Wang, H., Li, H. & Shao, M. A spectroscopic study of electrochemical nitrogen and nitrate reduction on rhodium surfaces. Angew. Chem. Int. Ed. 59, 10479–10483 (2020).

    Article  CAS  Google Scholar 

  45. Huang, J. et al. Potential-induced nanoclustering of metallic catalysts during electrochemical CO2 reduction. Nat. Commun. 9, 3117 (2018).

    Article  PubMed  PubMed Central  Google Scholar 

  46. Dovgolevsky, E. & Haick, H. Direct observation of the transition point between quasi-spherical and cubic nanoparticles in a two-step seed-mediated growth method. Small 4, 2059–2066 (2008).

    Article  CAS  PubMed  Google Scholar 

  47. Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996).

    Article  CAS  Google Scholar 

  48. Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).

    Article  CAS  Google Scholar 

  49. Hammer, B., Hansen, L. B. & Nørskov, J. K. Improved adsorption energetics within density-functional theory using revised Perdew–Burke–Ernzerhof functionals. Phys. Rev. B 59, 7413–7421 (1999).

    Article  Google Scholar 

Download references

Acknowledgements

H.Y.Z., Q.G., X.H., Y.L. and B.M. acknowledge funding support from the NSF CBET Catalysis CAREER programme (award number 2143710). This research used resources of the Advanced Photon Source, a US Department of Energy (DOE) Office of Science user facility operated for the DOE Office of Science by Argonne National Laboratory under contract number DE-AC02-06CH11357. Q.H. acknowledges the support of the National Research Foundation (NRF) Singapore, under its NRF Fellowship (NRF-NRFF11-2019-0002) and the Singapore Low-carbon Energy Research funding initiative (award number LCERFI01-0017). This research used the beamline 7-BM (QAS) of the National Synchrotron Light Source II, a US DOE Office of Science User Facility operated for the DOE Office of Science by the Brookhaven National Laboratory under contract number DE-SC0012704. S.Z. and S.-W.Y. gratefully acknowledge the financial support for this research provided by the NSF (grant number CBET-2004808). H.S.P and H.X. gratefully acknowledge the financial support of the NSF CAREER programme (CBET-1845531). The computational resource used in this work is provided by the advanced research computing at Virginia Polytechnic Institute and State University.

Author information

Author notes

  1. Huiyuan Zhu

    Present address: Department of Chemistry, University of Virginia, Charlottesville, VA, USA

  2. These authors contributed equally: Qiang Gao, Bingqing Yao, Hemanth Somarajan Pillai.

Authors and Affiliations

  1. Department of Chemical Engineering, Virginia Polytechnic Institute and State University, Blacksburg, VA, USA

    Qiang Gao, Hemanth Somarajan Pillai, Xue Han, Yuanqi Liu, Zihao Yan, Bokki Min, Hongliang Xin & Huiyuan Zhu

  2. Department of Materials Science and Engineering, National University of Singapore, Singapore, Singapore

    Bingqing Yao, Wenjie Zang & Qian He

  3. Department of Chemistry, University of Virginia, Charlottesville, VA, USA

    Shen-Wei Yu & Sen Zhang

  4. X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Lemont, IL, USA

    Hua Zhou

  5. National Synchrotron Light Source II (NSLS-II), Brookhaven National Laboratory, Upton, NY, USA

    Lu Ma

Authors
  1. Qiang Gao
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Bingqing Yao
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Hemanth Somarajan Pillai
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Wenjie Zang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Xue Han
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Yuanqi Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Shen-Wei Yu
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Zihao Yan
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Bokki Min
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Sen Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Hua Zhou
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Lu Ma
    View author publications

    You can also search for this author in PubMed Google Scholar

  13. Hongliang Xin
    View author publications

    You can also search for this author in PubMed Google Scholar

  14. Qian He
    View author publications

    You can also search for this author in PubMed Google Scholar

  15. Huiyuan Zhu
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

Q.G. and H.Y.Z. conceptualized the project. H.Y.Z. supervised the project. Q.G. planned and performed the catalyst synthesis, conducted the electrocatalytic tests, and collected and analysed the data. B.Y., W.Z. and Q.H. collected and analysed the STEM data. H.S.P. and H.X. did the theoretical calculations. X.H., Y.L., Z.Y. and B.M. helped with the synthesis of the catalysts and collected the data. S.-W.Y. and S.Z. helped to perform the DEMS and ATR-SEIRAS measurements. H.Z. performed the EXAFS measurements. L.M. performed the synchrotron X-ray diffraction measurements. Q.G., H.S.P., B.Y., Q.H., H.X. and H.Z. wrote the manuscript. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Hongliang Xin, Qian He or Huiyuan Zhu.

Ethics declarations

Competing interests

The authors declare no competing interests.

Peer review

Peer review information

Nature Synthesis thanks Minna Cao, Peng Zhang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary handling editor: Alexandra Groves, in collaboration with the Nature Synthesis team.

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 Figs. 1–34 and Tables 1–4.

Source data

Source Data Fig. 3

Structural characterizations.

Source Data Fig. 4

Electrocatalytic nitrate reduction performance.

Source Data Fig. 5

Density functional theory calculations.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and Permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Gao, Q., Yao, B., Pillai, H.S. et al. Synthesis of core/shell nanocrystals with ordered intermetallic single-atom alloy layers for nitrate electroreduction to ammonia. Nat. Synth (2023). https://doi.org/10.1038/s44160-023-00258-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1038/s44160-023-00258-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