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Title: Facet-specific oxidation of Mn(II) and heterogeneous growth of manganese (oxyhydr)oxides on hematite nanoparticles

Abstract

It is recognized that different facets of minerals vary distinctively in their chemical reactivity with aqueous solutions. However, detailed molecular and atomistic understandings of these phenomena are relatively limited. This study investigated the interaction of aqueous Mn2+ and dissolved oxygen on various facets of two morphology-types of iron oxide (hematite) nanocrystals. These interactions result in the oxidation of manganese and the heterogeneous nucleation and growth of Mn(II)/Mn(III), and Mn(III) oxides. The nanoscale morphology and atomic structure of the manganese oxide products were characterized in detail. Our results, for the first time, directly demonstrate the facet-dependent oxidation of Mn2+ and nucleation of Mn(II/III) oxides, followed by their epitaxial growth on hematite. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electron diffraction measurements reveal the growth of MnOx nanowires on {012} facets of both hematite nanoplates (HNP) and hematite nanocubes (HNC), while the basal {001} facets on the HNP particles do not produce precipitates. The average oxidation state of the MnOx on HNP and HNC determined using electron energy-loss spectroscopy (EELS) show that both Mn(II) and Mn(III) are present. The facet-dependent oxidation of Mn2+ may be attributed to adsorption-induced electron transfer (ET), and hematite {001} facets generally exhibiting weaker ability inmore » the uptake of ions relative to {012} facets, and the bulk ET from {012} to {001} facets through the conduction band of hematite. Nevertheless, the mineral composition and growth mechanisms of MnOx catalyzed by HNP and HNC are similar. High-resolution TEM analysis reveals the presence of both hausmannite and manganite on HNP and HNC. The nanoscale observations and thermodynamic considerations indicate that the growth mechanisms/processes of MnOx include heterogeneous nucleation of hausmannite nanoparticles, crystallization by particle attachment, transformation from hausmannite to manganite, and self-catalyzed MnOx growth. It is possible that all of these processes are concurrent. The crystallographic relationship between the heterogeneously formed manganite with hematite, which has not been reported before, proves that hematite provides reaction sites and functions as an atomic template for the formation of MnOx nanowires. These findings advance our understanding of the redox chemistry and heterogeneous growth of minerals as controlled by the surficial structure of the substrate mineral. This has important geochemical implications as the catalytic growth of less common, highly reactive phases like MnOx are known to be consequential in complex natural and anthropogenic environments.« less

Authors:
 [1]; ORCiD logo [2];  [1];  [1]; ORCiD logo [3]
+ Show Author Affiliations
  1. Chinese Academy of Sciences (CAS), Guangdong (China). Guangzhou Institute of Geochemistry, CAS Key Laboratory of Mineralogy and Metallogeny/Guangdong Provincial Key Laboratory of Mineral Physics and Materials; Chinese Academy of Sciences (CAS), Beijing (China)
  2. Univ. of Tokyo (Japan). Dept. of Earth and Planetary Science
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Earth and Environment Directorate; Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States). Dept. of Geosciences
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE; National Natural Science Foundation of China (NSFC); China Postdoctoral Foundation
OSTI Identifier:
1812531
Report Number(s):
PNNL-SA-158672
Journal ID: ISSN 0016-7037
Grant/Contract Number:  
AC05-76RL01830; 41872044; 41902040; 2019M663132
Resource Type:
Accepted Manuscript
Journal Name:
Geochimica et Cosmochimica Acta
Additional Journal Information:
Journal Volume: 307; Journal ID: ISSN 0016-7037
Publisher:
Elsevier; The Geochemical Society; The Meteoritical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Mn oxidation; manganese oxides; mineral nanoparticles; nanohematite; heterogeneous nucleation; manganese redox reactions

Citation Formats

Liu, Jing, Inoué, Sayako, Zhu, Runliang, He, Hongping, and Hochella, Michael F. Facet-specific oxidation of Mn(II) and heterogeneous growth of manganese (oxyhydr)oxides on hematite nanoparticles. United States: N. p., 2021. Web. doi:10.1016/j.gca.2021.05.043.
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Liu, Jing, Inoué, Sayako, Zhu, Runliang, He, Hongping, & Hochella, Michael F. Facet-specific oxidation of Mn(II) and heterogeneous growth of manganese (oxyhydr)oxides on hematite nanoparticles. United States. https://doi.org/10.1016/j.gca.2021.05.043
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Liu, Jing, Inoué, Sayako, Zhu, Runliang, He, Hongping, and Hochella, Michael F. Thu . "Facet-specific oxidation of Mn(II) and heterogeneous growth of manganese (oxyhydr)oxides on hematite nanoparticles". United States. https://doi.org/10.1016/j.gca.2021.05.043. https://www.osti.gov/servlets/purl/1812531.
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@article{osti_1812531,
title = {Facet-specific oxidation of Mn(II) and heterogeneous growth of manganese (oxyhydr)oxides on hematite nanoparticles},
author = {Liu, Jing and Inoué, Sayako and Zhu, Runliang and He, Hongping and Hochella, Michael F.},
abstractNote = {It is recognized that different facets of minerals vary distinctively in their chemical reactivity with aqueous solutions. However, detailed molecular and atomistic understandings of these phenomena are relatively limited. This study investigated the interaction of aqueous Mn2+ and dissolved oxygen on various facets of two morphology-types of iron oxide (hematite) nanocrystals. These interactions result in the oxidation of manganese and the heterogeneous nucleation and growth of Mn(II)/Mn(III), and Mn(III) oxides. The nanoscale morphology and atomic structure of the manganese oxide products were characterized in detail. Our results, for the first time, directly demonstrate the facet-dependent oxidation of Mn2+ and nucleation of Mn(II/III) oxides, followed by their epitaxial growth on hematite. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electron diffraction measurements reveal the growth of MnOx nanowires on {012} facets of both hematite nanoplates (HNP) and hematite nanocubes (HNC), while the basal {001} facets on the HNP particles do not produce precipitates. The average oxidation state of the MnOx on HNP and HNC determined using electron energy-loss spectroscopy (EELS) show that both Mn(II) and Mn(III) are present. The facet-dependent oxidation of Mn2+ may be attributed to adsorption-induced electron transfer (ET), and hematite {001} facets generally exhibiting weaker ability in the uptake of ions relative to {012} facets, and the bulk ET from {012} to {001} facets through the conduction band of hematite. Nevertheless, the mineral composition and growth mechanisms of MnOx catalyzed by HNP and HNC are similar. High-resolution TEM analysis reveals the presence of both hausmannite and manganite on HNP and HNC. The nanoscale observations and thermodynamic considerations indicate that the growth mechanisms/processes of MnOx include heterogeneous nucleation of hausmannite nanoparticles, crystallization by particle attachment, transformation from hausmannite to manganite, and self-catalyzed MnOx growth. It is possible that all of these processes are concurrent. The crystallographic relationship between the heterogeneously formed manganite with hematite, which has not been reported before, proves that hematite provides reaction sites and functions as an atomic template for the formation of MnOx nanowires. These findings advance our understanding of the redox chemistry and heterogeneous growth of minerals as controlled by the surficial structure of the substrate mineral. This has important geochemical implications as the catalytic growth of less common, highly reactive phases like MnOx are known to be consequential in complex natural and anthropogenic environments.},
doi = {10.1016/j.gca.2021.05.043},
journal = {Geochimica et Cosmochimica Acta},
number = ,
volume = 307,
place = {United States},
year = {Thu May 27 00:00:00 EDT 2021},
month = {Thu May 27 00:00:00 EDT 2021}
}
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