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Clays and Clay Minerals; June 2009; v. 57; no. 3; p. 353-360; DOI: 10.1346/CCMN.2009.0570307
© 2009 Clay Minerals Society
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FACTORS GOVERNING THE FORMATION OF LITHIOPHORITE AT ATMOSPHERIC PRESSURE

Haojie Cui1,2, Lei You1, Xionghan Feng1,*, Wenfeng Tan1, Guohong Qiu1 and Fan Liu1

1 Key Laboratory of Subtropical Agricultural Resources and Environment, Ministry of Agriculture, Huazhong Agricultural University, Wuhan 430070, China
2 Institute of Urban Environment, Chinese Academy of Science, Xiamen 361021, China

* E-mail address of corresponding author: fxh73{at}mail.hzau.edu.cn

Lithiophorite is a naturally occurring Mn oxide mineral commonly found in soils and sediments. The usual method of synthesizing lithiophorite is via a hydrothermal process in an autoclave at relatively high temperature and pressure. In the present study, an alternative, reflux method, at atmospheric pressure, for synthesis of lithiophorite was developed successfully. The influence of reaction duration, temperature, type of precursor birnessite (H-birnessite, Na-birnessite, aged Na-birnessite), and pH on the formation of lithiophorite were investigated by reflux treatment of lithium-aluminum hydroxide complex ion (LixAln(OH)mz+)-exchanged birnessite. The results show that the degree of conversion of lithiophorite decreases with decreasing reaction temperature. Lithiophorite can be obtained at pH values from 5.0 to 9.0, but a circumneutral pH is more favorable for formation at atmospheric pressure. Conversion of Na-birnessite (Bir-OH) to lithiophorite is more favored than aged Na-birnessite (Bir-OH-A). Lithiophorite was not obtained by refluxing the LixAln(OH)mz+ ion-exchanged H-birnessite (Bir-H) sample. The rate of conversion of lithiophorite increases with increasing reflux time. Lithiophorite synthesized by a reflux process has pseudo-hexagonal crystals of 0.1–0.5 µm with a chemical composition of Li0.24Al0.46MnO2.67(H2O)1.25. The results have important implications for the origin and underlying mechanism of lithiophorite formation in the environment.

Key Words: Birnessite • Lithiophorite • Manganese Oxide • Refluxing






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