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Birnessites with Different Average Manganese Oxidation States Synthesized, Characterized, and Transformed to Todorokite at Atmospheric Pressure

Published online by Cambridge University Press:  01 January 2024

Haojie Cui ,
Guohong Qiu ,
Xionghan Feng ,
Wenfeng Tan  and
Fan Liu
Haojie Cui
Affiliation:
Key Laboratory of Subtropical Agricultural Resources and Environment, Ministry of Agriculture, Huazhong Agricultural University, Wuhan 430070, China Institute of Urban Environment, Chinese Academy of Sciences, Xiamen 361021, China
Guohong Qiu
Affiliation:
Key Laboratory of Subtropical Agricultural Resources and Environment, Ministry of Agriculture, Huazhong Agricultural University, Wuhan 430070, China
Xionghan Feng
Affiliation:
Key Laboratory of Subtropical Agricultural Resources and Environment, Ministry of Agriculture, Huazhong Agricultural University, Wuhan 430070, China
Wenfeng Tan
Affiliation:
Key Laboratory of Subtropical Agricultural Resources and Environment, Ministry of Agriculture, Huazhong Agricultural University, Wuhan 430070, China
Fan Liu*
Affiliation:
Key Laboratory of Subtropical Agricultural Resources and Environment, Ministry of Agriculture, Huazhong Agricultural University, Wuhan 430070, China
*
* E-mail address of corresponding author: liufan@mail.hzau.edu.cn
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Abstract

Todorokite is a common manganese oxide mineral, with a tunnel structure, found in Earth surface environments, and is easily synthesized from layered birnessite. The aim of the current study was to prepare birnessites with different average manganese oxidation states (AOS) by controlling the MnO4−/Mn2+\$\end{document} ratio in concentrated NaOH or KOH. A series of (Na,K)-birnessites, Na-birnessites, and K-birnessites with different AOS was synthesized successfully in strongly alkaline media. The (Na,K)-birnessites and Na-birnessites prepared in NaOH clearly contained both large (500–1000 nm) and small (40–400 nm), plate-shaped crystallites. The K-birnessites prepared in KOH media consisted mostly of irregular (100–200 nm), plate-shaped crystallites. The degree of transformation of birnessite to todorokite at atmospheric pressure decreased as the AOS values of (Na,K)-birnessites and Na-birnessites increased from 3.51 to 3.80. No todorokite was present when a Na-birnessite with an AOS value of 3.87 was used as the precursor. Pyrophosphate, which is known to form strong complexes with Mn3+ at a pH range of 1–8, was added to a suspension of (Na,K)-birnessites in order to sequester the available Mn3+ in (Na,K)-birnessites. Removal of Mn3+ from birnessite MnO6 layers by pyrophosphate restricted transformation to todorokite — no (Na,K)-birnessite transformed to todorokite after pyrophosphate treatment. The interlayer K+ initially within (Na,K)-birnessites could not be completely ion-exchanged with Mg2+ to form todorokite at atmospheric pressure. No todorokite was forthcoming from K-birnessites even from those with small AOS values (3.50).

Keywords

AOSAtmospheric PressureBirnessiteTodorokite
Type
Research Article
Information
Clays and Clay Minerals , Volume 57 , Issue 6 , December 2009 , pp. 715 - 724
Copyright
Copyright © The Clay Minerals Society 2009

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