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Title: Hematite Crystallization from a Two-Line Ferrihydrite Suspension

Abstract

Rational design and synthesis of materials, determination of environmental conditions at the time of mineral formation, and definition of mechanisms in biomineralizing systems all require an understanding of the effect of multiple factors on modulating crystallization pathways. In this study, we investigate the influence of temperature, oxalate additive, aging time, and addition of seed crystals on hematite (α-Fe2O3, Hm) crystallization from a two-line ferrihydrite (Fe2O3·xH2O, Fh) suspension. We also investigate the effect of temperature on the aging of spindle-shaped Hm mesocrystals, which we synthesize through the addition of sodium oxalate. The results show that Hm mesocrystals form in a temperature window of 45 °C-130 °C. Temperatures ≥ 140 °C favor formation of rhombohedral Hm, suggesting classical monomer-by-monomer growth dominates, whereas crystallization by particle attachment (CPA) is dominant between 45 and 90 °C, while the two processes compete in the intermediate temperature range. Aging of mesocrystals in the original solution at 90 °C or 180 °C leads to a slow morphological evolution towards rhombohedral crystals due to Ostwald ripening. Then, by utilizing rhombohedral Hm and rod-shaped goethite as substrates on which to assemble the mesocrystals, we demonstrate formation of complex heterogeneous structures.

Authors:
ORCiD logo [1];  [1]
  1. Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); University of Washington, Seattle, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
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:
1958165
Report Number(s):
PNNL-SA-178244
Journal ID: ISSN 0013-4651
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 169; Journal Issue: 10; Journal ID: ISSN 0013-4651
Publisher:
IOP Publishing
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; hematite; crystallization; ferrihydrite; CPA; mesocrystal

Citation Formats

Zhu, Guomin, and De Yoreo, James J. Hematite Crystallization from a Two-Line Ferrihydrite Suspension. United States: N. p., 2022. Web. doi:10.1149/1945-7111/ac99a0.
Zhu, Guomin, & De Yoreo, James J. Hematite Crystallization from a Two-Line Ferrihydrite Suspension. United States. https://doi.org/10.1149/1945-7111/ac99a0
Zhu, Guomin, and De Yoreo, James J. Fri . "Hematite Crystallization from a Two-Line Ferrihydrite Suspension". United States. https://doi.org/10.1149/1945-7111/ac99a0. https://www.osti.gov/servlets/purl/1958165.
@article{osti_1958165,
title = {Hematite Crystallization from a Two-Line Ferrihydrite Suspension},
author = {Zhu, Guomin and De Yoreo, James J.},
abstractNote = {Rational design and synthesis of materials, determination of environmental conditions at the time of mineral formation, and definition of mechanisms in biomineralizing systems all require an understanding of the effect of multiple factors on modulating crystallization pathways. In this study, we investigate the influence of temperature, oxalate additive, aging time, and addition of seed crystals on hematite (α-Fe2O3, Hm) crystallization from a two-line ferrihydrite (Fe2O3·xH2O, Fh) suspension. We also investigate the effect of temperature on the aging of spindle-shaped Hm mesocrystals, which we synthesize through the addition of sodium oxalate. The results show that Hm mesocrystals form in a temperature window of 45 °C-130 °C. Temperatures ≥ 140 °C favor formation of rhombohedral Hm, suggesting classical monomer-by-monomer growth dominates, whereas crystallization by particle attachment (CPA) is dominant between 45 and 90 °C, while the two processes compete in the intermediate temperature range. Aging of mesocrystals in the original solution at 90 °C or 180 °C leads to a slow morphological evolution towards rhombohedral crystals due to Ostwald ripening. Then, by utilizing rhombohedral Hm and rod-shaped goethite as substrates on which to assemble the mesocrystals, we demonstrate formation of complex heterogeneous structures.},
doi = {10.1149/1945-7111/ac99a0},
journal = {Journal of the Electrochemical Society},
number = 10,
volume = 169,
place = {United States},
year = {Fri Oct 21 00:00:00 EDT 2022},
month = {Fri Oct 21 00:00:00 EDT 2022}
}

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