Nanocluster superstructures assembled via surface ligand switching at high temperature

Grayson Johnson; Moon Young Yang; Chang Liu; Hua Zhou; Xiaobing Zuo; Diane A. Dickie; Sihan Wang; Wenpei Gao; Bukuru Anaclet; Frédéric A. Perras; Fuyan Ma; Chenjie Zeng; Da Wang; Sara Bals; Sheng Dai; Zhen Xu; Guoliang Liu; William A. Goddard; Sen Zhang

doi:10.1038/s44160-023-00304-8

Nanocluster superstructures assembled via surface ligand switching at high temperature

Grayson Johnson, Moon Young Yang, Chang Liu, Hua Zhou, Xiaobing Zuo, Diane A. Dickie, Sihan Wang, Wenpei Gao, Bukuru Anaclet, Frédéric A. Perras, Fuyan Ma, Chenjie Zeng, Da Wang, Sara Bals, Sheng Dai, Zhen Xu, Guoliang Liu, William A. Goddard, Sen Zhang

Chemical Sciences Division

Research output: Contribution to journal › Article › peer-review

7 Scopus citations

Abstract

Superstructures with nanoscale building blocks, when coupled with precise control of the constituent units, open opportunities in rationally designing and manufacturing desired functional materials. Yet, synthetic strategies for the large-scale production of superstructures are scarce. We report a scalable and generalized approach to synthesizing superstructures assembled from atomically precise Ce₂₄O₂₈(OH)₈ and other rare-earth metal-oxide nanoclusters alongside a detailed description of the self-assembly mechanism. Combining operando small-angle X-ray scattering, ex situ molecular and structural characterizations, and molecular dynamics simulations indicates that a high-temperature ligand-switching mechanism, from oleate to benzoate, governs the formation of the nanocluster assembly. The chemical tuning of surface ligands controls superstructure disassembly and reassembly, and furthermore, enables the synthesis of multicomponent superstructures. This synthetic approach, and the accurate mechanistic understanding, are promising for the preparation of superstructures for use in electronics, plasmonics, magnetics and catalysis. [Figure not available: see fulltext.].

Original language	English
Pages (from-to)	828-837
Number of pages	10
Journal	Nature Synthesis
Volume	2
Issue number	9
DOIs	https://doi.org/10.1038/s44160-023-00304-8
State	Published - Sep 2023

Funding

This work was supported by the US National Science Foundation (CBET-2004808) and the Sloan Research Fellowship. We acknowledge UVA’s Nanoscale Material Characterization Facility (NMCF) for use of the XPS and SCXRD acquired under NSF MRI award DMR-1626201 and CHE-20188780, respectively. G.J. acknowledges support from the US Department of Energy (DOE), Office of Science, Office of Workforce Development for Teachers and Scientists, Office of Science Graduate Student Research (SCGSR) programme. The SCGSR programme is administered by the Oak Ridge Institute for Science and Education for the DOE under contract number DE‐SC0014664. This work benefited from the use of the SasView application, originally developed under NSF Award DMR-0520547. SasView also contains code developed with funding from the EU Horizon 2020 programme under the SINE2020 project grant number 654000. This research used resources of the Advanced Photon Source, a US DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory, under contract number DE-AC02-06CH11357. D.W. acknowledges an Individual Fellowship funded by the Marie Skłodowska-Curie Actions (MSCA) in the Horizon 2020 programme (grant 894254 SuprAtom). S.B. acknowledges support from the European Research Council (grant number 815128-REALNANO). The electron microscopy work was performed in part at the Analytical Instrumentation Facility (AIF) at North Carolina State University, which is supported by the State of North Carolina and the National Science Foundation (award number ECCS-2025064). The AIF is a member of the North Carolina Research Triangle Nanotechnology Network (RTNN), a site in the National Nanotechnology Coordinated Infrastructure (NNCI). G.L. gratefully acknowledges funding support by US NSF (DMR-1752611) and the Dean’s Discovery Fund at Virginia Tech. S.D. acknowledges support from the US DOE, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division. P. Bean at the University of Virginia is acknowledged for his SEM contributions measuring the HEASS. We thank T. B. Gunnoe (University of Virginia), J. Elena (University of Virginia), D. E. Jiang (University of California, Riverside) and C. B. Murray (University of Pennsylvania) for project discussions. This work was supported by the US National Science Foundation (CBET-2004808) and the Sloan Research Fellowship. We acknowledge UVA’s Nanoscale Material Characterization Facility (NMCF) for use of the XPS and SCXRD acquired under NSF MRI award DMR-1626201 and CHE-20188780, respectively. G.J. acknowledges support from the US Department of Energy (DOE), Office of Science, Office of Workforce Development for Teachers and Scientists, Office of Science Graduate Student Research (SCGSR) programme. The SCGSR programme is administered by the Oak Ridge Institute for Science and Education for the DOE under contract number DE‐SC0014664. This work benefited from the use of the SasView application, originally developed under NSF Award DMR-0520547. SasView also contains code developed with funding from the EU Horizon 2020 programme under the SINE2020 project grant number 654000. This research used resources of the Advanced Photon Source, a US DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory, under contract number DE-AC02-06CH11357. D.W. acknowledges an Individual Fellowship funded by the Marie Skłodowska-Curie Actions (MSCA) in the Horizon 2020 programme (grant 894254 SuprAtom). S.B. acknowledges support from the European Research Council (grant number 815128-REALNANO). The electron microscopy work was performed in part at the Analytical Instrumentation Facility (AIF) at North Carolina State University, which is supported by the State of North Carolina and the National Science Foundation (award number ECCS-2025064). The AIF is a member of the North Carolina Research Triangle Nanotechnology Network (RTNN), a site in the National Nanotechnology Coordinated Infrastructure (NNCI). G.L. gratefully acknowledges funding support by US NSF (DMR-1752611) and the Dean’s Discovery Fund at Virginia Tech. S.D. acknowledges support from the US DOE, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division. P. Bean at the University of Virginia is acknowledged for his SEM contributions measuring the HEASS. We thank T. B. Gunnoe (University of Virginia), J. Elena (University of Virginia), D. E. Jiang (University of California, Riverside) and C. B. Murray (University of Pennsylvania) for project discussions.

Funders	Funder number
Office of Science Graduate Student Research
SCGSR
National Science Foundation	DMR-1626201, CBET-2004808, DMR-1752611, ECCS-2025064, CHE-20188780
U.S. Department of Energy
Office of Science
Basic Energy Sciences
Workforce Development for Teachers and Scientists
Argonne National Laboratory	DE-AC02-06CH11357
Oak Ridge Institute for Science and Education	DMR-0520547, DE‐SC0014664
North Carolina State University
University of Virginia
Horizon 2020 Framework Programme	654000, 894254
H2020 Marie Skłodowska-Curie Actions
Division of Materials Sciences and Engineering
European Research Council	815128-REALNANO

Access to Document

10.1038/s44160-023-00304-8

Cite this

Johnson, G., Yang, M. Y., Liu, C., Zhou, H., Zuo, X., Dickie, D. A., Wang, S., Gao, W., Anaclet, B., Perras, F. A., Ma, F., Zeng, C., Wang, D., Bals, S., Dai, S., Xu, Z., Liu, G., Goddard, W. A., & Zhang, S. (2023). Nanocluster superstructures assembled via surface ligand switching at high temperature. Nature Synthesis, 2(9), 828-837. https://doi.org/10.1038/s44160-023-00304-8

@article{d6f008de1a9b428fb9e937beb9c5a27a,

title = "Nanocluster superstructures assembled via surface ligand switching at high temperature",

abstract = "Superstructures with nanoscale building blocks, when coupled with precise control of the constituent units, open opportunities in rationally designing and manufacturing desired functional materials. Yet, synthetic strategies for the large-scale production of superstructures are scarce. We report a scalable and generalized approach to synthesizing superstructures assembled from atomically precise Ce24O28(OH)8 and other rare-earth metal-oxide nanoclusters alongside a detailed description of the self-assembly mechanism. Combining operando small-angle X-ray scattering, ex situ molecular and structural characterizations, and molecular dynamics simulations indicates that a high-temperature ligand-switching mechanism, from oleate to benzoate, governs the formation of the nanocluster assembly. The chemical tuning of surface ligands controls superstructure disassembly and reassembly, and furthermore, enables the synthesis of multicomponent superstructures. This synthetic approach, and the accurate mechanistic understanding, are promising for the preparation of superstructures for use in electronics, plasmonics, magnetics and catalysis. [Figure not available: see fulltext.].",

author = "Grayson Johnson and Yang, {Moon Young} and Chang Liu and Hua Zhou and Xiaobing Zuo and Dickie, {Diane A.} and Sihan Wang and Wenpei Gao and Bukuru Anaclet and Perras, {Fr{\'e}d{\'e}ric A.} and Fuyan Ma and Chenjie Zeng and Da Wang and Sara Bals and Sheng Dai and Zhen Xu and Guoliang Liu and Goddard, {William A.} and Sen Zhang",

note = "Publisher Copyright: {\textcopyright} 2023, The Author(s), under exclusive licence to Springer Nature Limited.",

year = "2023",

month = sep,

doi = "10.1038/s44160-023-00304-8",

language = "English",

volume = "2",

pages = "828--837",

journal = "Nature Synthesis",

issn = "2731-0582",

publisher = "Nature Research",

number = "9",

}

TY - JOUR

T1 - Nanocluster superstructures assembled via surface ligand switching at high temperature

AU - Johnson, Grayson

AU - Yang, Moon Young

AU - Liu, Chang

AU - Zhou, Hua

AU - Zuo, Xiaobing

AU - Dickie, Diane A.

AU - Wang, Sihan

AU - Gao, Wenpei

AU - Anaclet, Bukuru

AU - Perras, Frédéric A.

AU - Ma, Fuyan

AU - Zeng, Chenjie

AU - Wang, Da

AU - Bals, Sara

AU - Dai, Sheng

AU - Xu, Zhen

AU - Liu, Guoliang

AU - Goddard, William A.

AU - Zhang, Sen

PY - 2023/9

Y1 - 2023/9

N2 - Superstructures with nanoscale building blocks, when coupled with precise control of the constituent units, open opportunities in rationally designing and manufacturing desired functional materials. Yet, synthetic strategies for the large-scale production of superstructures are scarce. We report a scalable and generalized approach to synthesizing superstructures assembled from atomically precise Ce24O28(OH)8 and other rare-earth metal-oxide nanoclusters alongside a detailed description of the self-assembly mechanism. Combining operando small-angle X-ray scattering, ex situ molecular and structural characterizations, and molecular dynamics simulations indicates that a high-temperature ligand-switching mechanism, from oleate to benzoate, governs the formation of the nanocluster assembly. The chemical tuning of surface ligands controls superstructure disassembly and reassembly, and furthermore, enables the synthesis of multicomponent superstructures. This synthetic approach, and the accurate mechanistic understanding, are promising for the preparation of superstructures for use in electronics, plasmonics, magnetics and catalysis. [Figure not available: see fulltext.].

AB - Superstructures with nanoscale building blocks, when coupled with precise control of the constituent units, open opportunities in rationally designing and manufacturing desired functional materials. Yet, synthetic strategies for the large-scale production of superstructures are scarce. We report a scalable and generalized approach to synthesizing superstructures assembled from atomically precise Ce24O28(OH)8 and other rare-earth metal-oxide nanoclusters alongside a detailed description of the self-assembly mechanism. Combining operando small-angle X-ray scattering, ex situ molecular and structural characterizations, and molecular dynamics simulations indicates that a high-temperature ligand-switching mechanism, from oleate to benzoate, governs the formation of the nanocluster assembly. The chemical tuning of surface ligands controls superstructure disassembly and reassembly, and furthermore, enables the synthesis of multicomponent superstructures. This synthetic approach, and the accurate mechanistic understanding, are promising for the preparation of superstructures for use in electronics, plasmonics, magnetics and catalysis. [Figure not available: see fulltext.].

UR - http://www.scopus.com/inward/record.url?scp=85169888059&partnerID=8YFLogxK

U2 - 10.1038/s44160-023-00304-8

DO - 10.1038/s44160-023-00304-8

M3 - Article

AN - SCOPUS:85169888059

SN - 2731-0582

VL - 2

SP - 828

EP - 837

JO - Nature Synthesis

JF - Nature Synthesis

IS - 9

ER -

Nanocluster superstructures assembled via surface ligand switching at high temperature

Abstract

Funding

Access to Document

Other files and links

Fingerprint

Cite this