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Highly luminescent and catalytically active suprastructures of magic-sized semiconductor nanoclusters

Nature Materials volume 20, pages 650–657 (2021)Cite this article

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Abstract

Metal chalcogenide magic-sized nanoclusters have shown intriguing photophysical and chemical properties, yet ambient instability has hampered their extensive applications. Here we explore the periodic assembly of these nanoscale building blocks through organic linkers to overcome such limitations and further boost their properties. We designed a diamine-based heat-up self-assembly process to assemble Mn2+:(CdSe)13 and Mn2+:(ZnSe)13 magic-sized nanoclusters into three- and two-dimensional suprastructures, respectively, obtaining enhanced stability and solid-state photoluminescence quantum yields (from <1% for monoamine-based systems to ~72% for diamine-based suprastructures). We also exploited the atomic-level miscibility of Cd and Zn to synthesize Mn2+:(Cd1−xZnxSe)13 alloy suprastructures with tunable metal synergy: Mn2+:(Cd0.5Zn0.5Se)13 suprastructures demonstrated high catalytic activity (turnover number, 17,964 per cluster in 6 h; turnover frequency, 2,994 per cluster per hour) for converting CO2 to organic cyclic carbonates under mild reaction conditions. The enhanced stability, photoluminescence and catalytic activity through combined cluster-assembly and metal synergy advance the usability of inorganic semiconductor nanoclusters.

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Fig. 1: Schematic representation of the unique growth pathways of MSCs.
Fig. 2: Morphology characterization of SSs of MSCs and NRs.
Fig. 3: Optical and photophysical properties of MSCs and their SSs.
Fig. 4: Ambient stability and photostability comparison.
Fig. 5: Catalytic performance of SSs of MSCs.

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Data availability

Source data are provided with this paper. Image datasets in the main text and all the data in the Supplementary Information are available from the corresponding author upon reasonable request.

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Acknowledgements

T.H. acknowledges the financial support by the Research Center Program of the IBS (IBS-R006-D1) in Korea. D.R.G. acknowledges support from the US National Science Foundation (NSF) through the UW Molecular Engineering Materials Center, a Materials Research Science and Engineering Center (DMR-1719797), and through project DMR-1807394. This research was also supported by the Clean Energy Institute at the University of Washington.

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Author notes

  1. These authors contributed equally: Woonhyuk Baek, Megalamane S. Bootharaju.

Authors and Affiliations

  1. Center for Nanoparticle Research, Institute for Basic Science (IBS), Seoul, Republic of Korea

    Woonhyuk Baek, Megalamane S. Bootharaju, Sanghwa Lee & Taeghwan Hyeon

  2. School of Chemical and Biological Engineering, and Institute of Chemical Processes, Seoul National University, Seoul, Republic of Korea

    Woonhyuk Baek, Megalamane S. Bootharaju, Sanghwa Lee & Taeghwan Hyeon

  3. Department of Chemistry, University of Washington, Seattle, WA, USA

    Kelly M. Walsh & Daniel R. Gamelin

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Contributions

W.B., M.S.B. and T.H. conceived the research. W.B. and M.S.B. designed the experiments. W.B., M.S.B., K.M.W. and S.L. performed experiments and analysed the results. K.M.W. determined PLQY values and performed temperature-dependent PL and lifetime experiments. M.S.B. and W.B. performed catalytic CO2 conversion. S.L. conducted the HAADF-STEM and EDS analysis. W.B., M.S.B., K.M.W., S.L., D.R.G. and T.H. wrote the manuscript. T.H. supervised the project. All authors commented on the manuscript.

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Correspondence to Taeghwan Hyeon.

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Peer review information Nature Materials thanks Raffaella Buonsanti and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Information

Supplementary Sections 1–40, including Supplementary Figs. 1–34, Tables 1–4 and refs. 1–18.

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Baek, W., Bootharaju, M.S., Walsh, K.M. et al. Highly luminescent and catalytically active suprastructures of magic-sized semiconductor nanoclusters. Nat. Mater. 20, 650–657 (2021). https://doi.org/10.1038/s41563-020-00880-6

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