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Title: Revealing the Effects of the Non-solvent on the Ligand Shell of Nanoparticles and Their Crystallization

Abstract

When nanoparticles (NPs) are assembled from solution, a common assembly method of choice is either solution destabilization or solvent evaporation technique. The destabilization of the NP solution by non-solvents results in the formation of faceted supercrystals (SCs) while periodic film-like assemblies are typically formed by solvent evaporation. In this article, we reveal the effect of non-solvents in washing, dispersing, and crystallizing NPs. Small angle neutron scattering (SANS) is employed for monitoring the ligand shell of NPs in solutions upon introduction of various non-solvents. The SC crystallization process is traced in situ with small-angle X-ray scattering (SAXS), and the structures of the resulting single-crystalline SCs are examined in detail by mapping the reciprocal space using SAXS and wide-angle X-ray scattering. Our study suggests that the relative miscibility of the non-solvent with solvents and ligands 4111 determines the solvation and thickness of the ligand shell and thereby the resulting structure of SCs. In the early stage of crystallization, truncated octahedral PbS NPs form SCs with face-centered cubic (fcc) symmetry. In the later stage, the fcc symmetry is preserved in the SC formed by larger (5.60 nm) NPs, but the SC assembled from smaller (4.14 nm) NPs undergoes a phase transition into body-centeredmore » cubic (bcc) lattice via Bain transformation, becoming a polycrystalline SC containing three structurally correlated bcc domains and one untransformed fcc domain. Our study provides the detailed understanding of the non-solvent effect that impacts beyond the formation of SCs, enabling the judicious selection of solvent/non-solvent mixtures for NP purification.« less

Authors:
ORCiD logo [1];  [2];  [3]; ORCiD logo [4]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials; Wuhan Univ. (China)
  4. Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS) amd Center for Nanoscale Materials (CNM)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1607372
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 141; Journal Issue: 42; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; SAXS; colloidal solution destabilization; nanoparticles; reciprocal space mapping; self-assembly; solvent ligand interaction; supercrystal

Citation Formats

Lee, Byeongdu, Littrell, Kenneth, Sha, Yuchen, and Shevchenko, Elena V. Revealing the Effects of the Non-solvent on the Ligand Shell of Nanoparticles and Their Crystallization. United States: N. p., 2019. Web. doi:10.1021/jacs.9b06010.
Lee, Byeongdu, Littrell, Kenneth, Sha, Yuchen, & Shevchenko, Elena V. Revealing the Effects of the Non-solvent on the Ligand Shell of Nanoparticles and Their Crystallization. United States. https://doi.org/10.1021/jacs.9b06010
Lee, Byeongdu, Littrell, Kenneth, Sha, Yuchen, and Shevchenko, Elena V. 2019. "Revealing the Effects of the Non-solvent on the Ligand Shell of Nanoparticles and Their Crystallization". United States. https://doi.org/10.1021/jacs.9b06010. https://www.osti.gov/servlets/purl/1607372.
@article{osti_1607372,
title = {Revealing the Effects of the Non-solvent on the Ligand Shell of Nanoparticles and Their Crystallization},
author = {Lee, Byeongdu and Littrell, Kenneth and Sha, Yuchen and Shevchenko, Elena V.},
abstractNote = {When nanoparticles (NPs) are assembled from solution, a common assembly method of choice is either solution destabilization or solvent evaporation technique. The destabilization of the NP solution by non-solvents results in the formation of faceted supercrystals (SCs) while periodic film-like assemblies are typically formed by solvent evaporation. In this article, we reveal the effect of non-solvents in washing, dispersing, and crystallizing NPs. Small angle neutron scattering (SANS) is employed for monitoring the ligand shell of NPs in solutions upon introduction of various non-solvents. The SC crystallization process is traced in situ with small-angle X-ray scattering (SAXS), and the structures of the resulting single-crystalline SCs are examined in detail by mapping the reciprocal space using SAXS and wide-angle X-ray scattering. Our study suggests that the relative miscibility of the non-solvent with solvents and ligands 4111 determines the solvation and thickness of the ligand shell and thereby the resulting structure of SCs. In the early stage of crystallization, truncated octahedral PbS NPs form SCs with face-centered cubic (fcc) symmetry. In the later stage, the fcc symmetry is preserved in the SC formed by larger (5.60 nm) NPs, but the SC assembled from smaller (4.14 nm) NPs undergoes a phase transition into body-centered cubic (bcc) lattice via Bain transformation, becoming a polycrystalline SC containing three structurally correlated bcc domains and one untransformed fcc domain. Our study provides the detailed understanding of the non-solvent effect that impacts beyond the formation of SCs, enabling the judicious selection of solvent/non-solvent mixtures for NP purification.},
doi = {10.1021/jacs.9b06010},
url = {https://www.osti.gov/biblio/1607372}, journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 42,
volume = 141,
place = {United States},
year = {Wed Sep 25 00:00:00 EDT 2019},
month = {Wed Sep 25 00:00:00 EDT 2019}
}

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Cited by: 26 works
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Works referencing / citing this record: