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

Nature Synthesis volume 2, pages 624–634 (2023)Cite this article

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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.

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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.

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

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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

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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.

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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.

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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.

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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 2, 624–634 (2023). https://doi.org/10.1038/s44160-023-00258-x

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