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

Journal Article · · Environmental Science and Technology

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.

Research Organization:
Univ. of Connecticut, Storrs, CT (United States)
Sponsoring Organization:
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
Grant/Contract Number:
FG02-86ER13622; 41571228; 41425006; 2017YFD0801000
OSTI ID:
1598154
Journal Information:
Environmental Science and Technology, Vol. 52, Issue 12; ISSN 0013-936X
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 33 works
Citation information provided by
Web of Science