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Title: Effects of Co doping on the structure and physicochemical properties of hausmannite (Mn3O4) and its transformation during aging

Abstract

Hausmannite is a common low-valence manganese oxide mineral with a distorted spinel structure in surficial sediments. Although natural Mn oxides often contain various transition metal (TM) impurities, few studies have addressed the substitution mechanisms of TMs, such as cobalt (Co), with hausmannite and induced changes in the mineral physicochemical properties. In this study, Co-doped hausmannites with final Co/Mn molar ratios of 0.05 and 0.11 were synthesized and characterized by wet chemical analysis, powder X-ray diffraction (XRD), Fourier transformed infrared spectra (FTIR), high resolution transmission electron microscope (HRTEM), X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure spectroscopy (XAFS). Co-doped samples have larger crystallite sizes and smaller specific surface areas than those of the hausmannite without Co. The Co cations exist in a mixed-valence of +3 and + 2. Powder XRD and acid dissolution experiments indicate that Co incorporates into the mineral structures, and increases the mineral structural stability. Co K-edge extended X-ray adsorption fine structure (EXAFS) analysis demonstrates that Co likely substitutes for lattice Mn(III). After aging at room temperature for three years, 14.1 ± 1.9% of pure hausmannite is transformed to manganite while only 2.6 ± 0.7% of manganite appears in the aged Co-doped sample with an initial Co/Mnmore » molar ratio of 0.10. Finally, these results provide new insights into the incorporation mechanisms of TMs into low valence Mn oxides, and the stability of these minerals in natural environments.« less

Authors:
 [1];  [2];  [3];  [4];  [5];  [6];  [1];  [7];  [7];  [1];  [1]
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  1. Huazhong Agricultural University, Wuhan (China)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Zhejiang Univ. of Technology, Hangzhou (China)
  4. Smithsonian Institute, Washington, DC (United States)
  5. Univ. of Grenoble Alpes, (France)
  6. Rutgers University, Newark, NJ (United States)
  7. Inner Mongolia Univ., Hohhot (China)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE; National Natural Science Foundation of China (NSFC); National Key Research and Development Program of China; Fundamental Research Funds for the Central Universities
OSTI Identifier:
1830113
Grant/Contract Number:  
AC05-00OR22725; 42077015; 41771267; 2016YFD0800403; 103-510320036
Resource Type:
Accepted Manuscript
Journal Name:
Chemical Geology
Additional Journal Information:
Journal Volume: 582; Journal ID: ISSN 0009-2541
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 58 GEOSCIENCES; Mn oxide; Hausmannite; Transition metal; Cobalt; Transformation

Citation Formats

Zhang, Shuang, Li, Hui, Wu, Zhongkuan, Post, Jeffrey E., Lanson, Bruno, Elzinga, Evert J., Liu, Yurong, Li, Haigang, Hong, Mei, Liu, Fan, and Yin, Hui. Effects of Co doping on the structure and physicochemical properties of hausmannite (Mn3O4) and its transformation during aging. United States: N. p., 2021. Web. doi:10.1016/j.chemgeo.2021.120448.
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Zhang, Shuang, Li, Hui, Wu, Zhongkuan, Post, Jeffrey E., Lanson, Bruno, Elzinga, Evert J., Liu, Yurong, Li, Haigang, Hong, Mei, Liu, Fan, & Yin, Hui. Effects of Co doping on the structure and physicochemical properties of hausmannite (Mn3O4) and its transformation during aging. United States. https://doi.org/10.1016/j.chemgeo.2021.120448
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Zhang, Shuang, Li, Hui, Wu, Zhongkuan, Post, Jeffrey E., Lanson, Bruno, Elzinga, Evert J., Liu, Yurong, Li, Haigang, Hong, Mei, Liu, Fan, and Yin, Hui. Wed . "Effects of Co doping on the structure and physicochemical properties of hausmannite (Mn3O4) and its transformation during aging". United States. https://doi.org/10.1016/j.chemgeo.2021.120448. https://www.osti.gov/servlets/purl/1830113.
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@article{osti_1830113,
title = {Effects of Co doping on the structure and physicochemical properties of hausmannite (Mn3O4) and its transformation during aging},
author = {Zhang, Shuang and Li, Hui and Wu, Zhongkuan and Post, Jeffrey E. and Lanson, Bruno and Elzinga, Evert J. and Liu, Yurong and Li, Haigang and Hong, Mei and Liu, Fan and Yin, Hui},
abstractNote = {Hausmannite is a common low-valence manganese oxide mineral with a distorted spinel structure in surficial sediments. Although natural Mn oxides often contain various transition metal (TM) impurities, few studies have addressed the substitution mechanisms of TMs, such as cobalt (Co), with hausmannite and induced changes in the mineral physicochemical properties. In this study, Co-doped hausmannites with final Co/Mn molar ratios of 0.05 and 0.11 were synthesized and characterized by wet chemical analysis, powder X-ray diffraction (XRD), Fourier transformed infrared spectra (FTIR), high resolution transmission electron microscope (HRTEM), X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure spectroscopy (XAFS). Co-doped samples have larger crystallite sizes and smaller specific surface areas than those of the hausmannite without Co. The Co cations exist in a mixed-valence of +3 and + 2. Powder XRD and acid dissolution experiments indicate that Co incorporates into the mineral structures, and increases the mineral structural stability. Co K-edge extended X-ray adsorption fine structure (EXAFS) analysis demonstrates that Co likely substitutes for lattice Mn(III). After aging at room temperature for three years, 14.1 ± 1.9% of pure hausmannite is transformed to manganite while only 2.6 ± 0.7% of manganite appears in the aged Co-doped sample with an initial Co/Mn molar ratio of 0.10. Finally, these results provide new insights into the incorporation mechanisms of TMs into low valence Mn oxides, and the stability of these minerals in natural environments.},
doi = {10.1016/j.chemgeo.2021.120448},
journal = {Chemical Geology},
number = ,
volume = 582,
place = {United States},
year = {Wed Jul 21 00:00:00 EDT 2021},
month = {Wed Jul 21 00:00:00 EDT 2021}
}
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