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Title: Photochemical Formation and Transformation of Birnessite: Effects of Cations on Micromorphology and Crystal Structure

Abstract

As important components with excellent oxidation and adsorption activity in soils and sediments, manganese oxides affect the transportation and fate of nutrients and pollutants in natural environments. In this work, birnessite was formed by photocatalytic oxidation of Mn2+aq in the presence of nitrate under solar irradiation. The effects of concentrations and species of interlayer cations (Na+, Mg2+, and K+) on birnessite crystal structure and micromorphology were investigated. The roles of adsorbed Mn2+ and pH in the transformation of the photosynthetic birnessite were further studied. The results indicated that Mn2+aq was oxidized to birnessite by superoxide radicals (O2•–) generated from the photolysis of NO3 under UV irradiation. The particle size and thickness of birnessite decreased with increasing cation concentration. The birnessite showed a plate-like morphology in the presence of K+, while exhibited a rumpled sheet-like morphology when Na+ or Mg2+ was used. The different micromorphologies of birnessites could be ascribed to the position of cations in the interlayer. The adsorbed Mn2+ and high pH facilitated the reduction of birnessite to low-valence manganese oxides including hausmannite, feitknechtite, and manganite. Finally, this study suggests that interlayer cations and Mn2+ play essential roles in the photochemical formation and transformation of birnessite in aqueous environments.

Authors:
 [1];  [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1];  [1]
  1. Huazhong Agricultural Univ., Wuhan (China)
  2. Univ. of Connecticut, Storrs, CT (United States)
Publication Date:
Research Org.:
Univ. of Connecticut, Storrs, CT (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Natural Science Foundation of China (NSFC); National Key Research and Development Program of China; Fok Ying-Tong Education Foundation
OSTI Identifier:
1598154
Grant/Contract Number:  
FG02-86ER13622; 41571228; 41425006; 2017YFD0801000
Resource Type:
Accepted Manuscript
Journal Name:
Environmental Science and Technology
Additional Journal Information:
Journal Volume: 52; Journal Issue: 12; Journal ID: ISSN 0013-936X
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; oxides; layered materials; oxidation; transition metals; cations

Citation Formats

Zhang, Tengfei, Liu, Lihu, Tan, Wenfeng, Suib, Steven L., Qiu, Guohong, and Liu, Fan. Photochemical Formation and Transformation of Birnessite: Effects of Cations on Micromorphology and Crystal Structure. United States: N. p., 2018. Web. https://doi.org/10.1021/acs.est.7b06592.
Zhang, Tengfei, Liu, Lihu, Tan, Wenfeng, Suib, Steven L., Qiu, Guohong, & Liu, Fan. Photochemical Formation and Transformation of Birnessite: Effects of Cations on Micromorphology and Crystal Structure. United States. https://doi.org/10.1021/acs.est.7b06592
Zhang, Tengfei, Liu, Lihu, Tan, Wenfeng, Suib, Steven L., Qiu, Guohong, and Liu, Fan. Thu . "Photochemical Formation and Transformation of Birnessite: Effects of Cations on Micromorphology and Crystal Structure". United States. https://doi.org/10.1021/acs.est.7b06592. https://www.osti.gov/servlets/purl/1598154.
@article{osti_1598154,
title = {Photochemical Formation and Transformation of Birnessite: Effects of Cations on Micromorphology and Crystal Structure},
author = {Zhang, Tengfei and Liu, Lihu and Tan, Wenfeng and Suib, Steven L. and Qiu, Guohong and Liu, Fan},
abstractNote = {As important components with excellent oxidation and adsorption activity in soils and sediments, manganese oxides affect the transportation and fate of nutrients and pollutants in natural environments. In this work, birnessite was formed by photocatalytic oxidation of Mn2+aq in the presence of nitrate under solar irradiation. The effects of concentrations and species of interlayer cations (Na+, Mg2+, and K+) on birnessite crystal structure and micromorphology were investigated. The roles of adsorbed Mn2+ and pH in the transformation of the photosynthetic birnessite were further studied. The results indicated that Mn2+aq was oxidized to birnessite by superoxide radicals (O2•–) generated from the photolysis of NO3– under UV irradiation. The particle size and thickness of birnessite decreased with increasing cation concentration. The birnessite showed a plate-like morphology in the presence of K+, while exhibited a rumpled sheet-like morphology when Na+ or Mg2+ was used. The different micromorphologies of birnessites could be ascribed to the position of cations in the interlayer. The adsorbed Mn2+ and high pH facilitated the reduction of birnessite to low-valence manganese oxides including hausmannite, feitknechtite, and manganite. Finally, this study suggests that interlayer cations and Mn2+ play essential roles in the photochemical formation and transformation of birnessite in aqueous environments.},
doi = {10.1021/acs.est.7b06592},
journal = {Environmental Science and Technology},
number = 12,
volume = 52,
place = {United States},
year = {2018},
month = {5}
}

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