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Title: Self-similar mesocrystals form via interface-driven nucleation and assembly

Abstract

Crystallization by particle attachment (CPA) is a frequently occurring mechanism of colloidal crystallization that results in hierarchical morphologies. CPA has been exploited to create nanomaterials with unusual properties and is implicated in the development of complex mineral textures. Oriented attachment–a form of CPA in which particles align along specific crystallographic directions–produces mesocrystals that diffract as single crystals do, although the constituent particles are still discernible. The conventional view of CPA is that nucleation provides a supply of particles that aggregate via Brownian motion biased by attractive interparticle potentials. However, mesocrystals often exhibit regular morphologies and uniform sizes. Although many crystal systems form mesocrystals and individual attachment events have been directly visualized10, how random attachment events lead to well defined, self-similar morphologies remains unknown, as does the role of surface-bound ligands, which are ubiquitous in nanoparticle systems. Attempts to understand mesocrystal formation are further complicated in many systems by the presence of precursor nanoparticles with a phase distinct from that of the bulk. Some studies propose that such particles convert before attachment, whereas others attribute conversion to the attachment process itself and yet others conclude that transformation occurs after the mesocrystals exceed a characteristic size. Here we investigate mesocrystal formation bymore » iron oxides, which are important colloidal phases in natural environments and classic examples of systems forming ubiquitous precursor phases and undergoing CPA accompanied by phase transformations. Combining in situ transmission electron microscopy (TEM) at 80 degrees Celsius with ‘freeze-and-look’ TEM, we tracked the formation of haematite (Hm) mesocrystals in the presence of oxalate (Ox), which is abundant in soils, where iron oxides are common. In this work, we find that isolated Hm particles rarely appear, but once formed, interfacial gradients at the Ox-covered surfaces drive Hm particles to nucleate repeatedly about two nanometres from the surfaces, to which they then attach, thereby generating mesocrystals. Comparison to natural and synthetic systems suggests that interface-driven pathways are widespread.« less

Authors:
 [1]; ORCiD logo [2];  [2];  [2];  [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2];  [1]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Univ. of Washington, Seattle, WA (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1781651
Report Number(s):
PNNL-SA-157135
Journal ID: ISSN 0028-0836
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Nature (London)
Additional Journal Information:
Journal Name: Nature (London); Journal Volume: 590; Journal Issue: 7846; Journal ID: ISSN 0028-0836
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Materials chemistry; Materials science; Nanoscale materials; Nanoscience and technology; Synthesis and processing

Citation Formats

Zhu, Guomin, Sushko, Maria L., Loring, John S., Legg, Benjamin A., Song, Miao, Soltis, Jennifer A., Huang, Xiaopeng, Rosso, Kevin M., and De Yoreo, James J. Self-similar mesocrystals form via interface-driven nucleation and assembly. United States: N. p., 2021. Web. doi:10.1038/s41586-021-03300-0.
Zhu, Guomin, Sushko, Maria L., Loring, John S., Legg, Benjamin A., Song, Miao, Soltis, Jennifer A., Huang, Xiaopeng, Rosso, Kevin M., & De Yoreo, James J. Self-similar mesocrystals form via interface-driven nucleation and assembly. United States. https://doi.org/10.1038/s41586-021-03300-0
Zhu, Guomin, Sushko, Maria L., Loring, John S., Legg, Benjamin A., Song, Miao, Soltis, Jennifer A., Huang, Xiaopeng, Rosso, Kevin M., and De Yoreo, James J. Wed . "Self-similar mesocrystals form via interface-driven nucleation and assembly". United States. https://doi.org/10.1038/s41586-021-03300-0. https://www.osti.gov/servlets/purl/1781651.
@article{osti_1781651,
title = {Self-similar mesocrystals form via interface-driven nucleation and assembly},
author = {Zhu, Guomin and Sushko, Maria L. and Loring, John S. and Legg, Benjamin A. and Song, Miao and Soltis, Jennifer A. and Huang, Xiaopeng and Rosso, Kevin M. and De Yoreo, James J.},
abstractNote = {Crystallization by particle attachment (CPA) is a frequently occurring mechanism of colloidal crystallization that results in hierarchical morphologies. CPA has been exploited to create nanomaterials with unusual properties and is implicated in the development of complex mineral textures. Oriented attachment–a form of CPA in which particles align along specific crystallographic directions–produces mesocrystals that diffract as single crystals do, although the constituent particles are still discernible. The conventional view of CPA is that nucleation provides a supply of particles that aggregate via Brownian motion biased by attractive interparticle potentials. However, mesocrystals often exhibit regular morphologies and uniform sizes. Although many crystal systems form mesocrystals and individual attachment events have been directly visualized10, how random attachment events lead to well defined, self-similar morphologies remains unknown, as does the role of surface-bound ligands, which are ubiquitous in nanoparticle systems. Attempts to understand mesocrystal formation are further complicated in many systems by the presence of precursor nanoparticles with a phase distinct from that of the bulk. Some studies propose that such particles convert before attachment, whereas others attribute conversion to the attachment process itself and yet others conclude that transformation occurs after the mesocrystals exceed a characteristic size. Here we investigate mesocrystal formation by iron oxides, which are important colloidal phases in natural environments and classic examples of systems forming ubiquitous precursor phases and undergoing CPA accompanied by phase transformations. Combining in situ transmission electron microscopy (TEM) at 80 degrees Celsius with ‘freeze-and-look’ TEM, we tracked the formation of haematite (Hm) mesocrystals in the presence of oxalate (Ox), which is abundant in soils, where iron oxides are common. In this work, we find that isolated Hm particles rarely appear, but once formed, interfacial gradients at the Ox-covered surfaces drive Hm particles to nucleate repeatedly about two nanometres from the surfaces, to which they then attach, thereby generating mesocrystals. Comparison to natural and synthetic systems suggests that interface-driven pathways are widespread.},
doi = {10.1038/s41586-021-03300-0},
journal = {Nature (London)},
number = 7846,
volume = 590,
place = {United States},
year = {Wed Feb 17 00:00:00 EST 2021},
month = {Wed Feb 17 00:00:00 EST 2021}
}

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