Abstract
Birnessite can be used as a precursor in the preparation of manganese oxides. Synthesis of pure birnessite is difficult because of a side reaction, which yields hausmannite. This study aimed to develop a modified oxidation-deprotonation reaction (ODPR) method to eliminate the formation of hausmannite, and to investigate the influence of alkalinity on the synthetic products. In contrast to the conventional synthesis of birnessite through oxygen or permanganate oxidation, the ODPR method can produce birnessite without any impurities, within 5 h, and in a reproducible fashion. The distinctive feature of the ODPR method is the bubbling of N2 gas into NaOH and Mn2+ solutions before mixing the NaOH with Mn2+, in order to keep oxygen away from each solution. As soon as white pyrochroite was formed, oxygen gas was forced in as an oxidant to initiate the oxidation reaction. A black suspension with a blue tint appeared after 5 h of reaction. These precipitates were collected and examined by X-ray diffraction (XRD), scanning electron microscopy (SEM), infrared (IR) and Raman spectroscopy. The average oxidation state of the Mn oxides was also determined. The results showed that pure birnessite with good crystallinity was formed. Oxidation of 1 M NaOH mixed with Mn2+ solution formed random-stacked birnessite. However, the oxidation of 4 M NaOH mixed with Mn2+ formed birnessite. Random-stacked birnessite can be transformed into birnessite by ageing suspensions at 313 to 373 K.
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References
Burns, R.G., Burns, V.M. and Stockman, H.W. (1983) A review of the todorokite–buserite problem: Implications to the mineralogy of marine manganese nodules. American Mineralogist, 68, 972–980.
Chen, C.C., Golden, D.C. and Dixon, J.B. (1986) Transformation of synthetic birnessite to cryptomelane: An electron microscopy study. Clays and Clay Minerals, 34, 565–571.
Ching, S., Landrigan, J.A. and Jørgensen, M.L. (1995) Sol-gel synthesis of birnessite from KMnO4 and simple sugar. Chemistry of Materials, 7, 1064–1066.
Ching, S., Petrovay, D.J., Jorgensen, M.L. and Suib, S.L. (1997) Sol-gel synthesis of layered birnessite-type manganese oxides. Inorganic Chemistry, 36, 883–890.
Cornell, R.M. and Giovanoli, R. (1988) Transformation of hausmmanite into birnessite in alkaline media. Clays and Clay Minerals, 36, 249–257.
Drits, V.A., Silvester, E., Gorshkov, A.I. and Manceau, A. (1997) Structure of synthetic monoclinic Na-rich birnessite and hexagonal birnessite: I. Results from X-ray diffraction and selected-area electron diffraction. American Mineralogist, 82, 946–961.
Giovanoli, R. (1980) Vernadite is random-stacked birnessite. Mineralium Deposita, 14, 249–261.
Giovanoli, R. (1985) Layer structures and tunnel structures in manganates. Chemie der Erde, 44, 227–244.
Giovanoli, R., Stahli, E. and Feitknecht, W. (1970a) Ueber oxidhydroxide des vierwertigen mangans mit schichtengitter. 1. Mitteilung: Natriummangan (II, III) manganat(IV). Helvetica Chimica Acta, 53, 209–220.
Giovanoli, R., Stahli, E. and Feitknecht, W. (1970b) Ueber oxidhydroxide des vierwertigen mangans mit schichtengitter. 1. Mitteilung: Natriummangan (II, III) manganat(IV). Helvetica Chimica Acta, 53, 453–464.
Golden, D.C., Dixon, J.B. and Chen, C.C. (1986) Ion exchange, thermal transformations, and oxidizing properties of birnessite. Clays and Clay Minerals, 34, 511–520.
Golden, D.C., Chen, C.C. and Dixon, J.B. (1987) Transformation of birnessite to buserite, todorokite, and manganite under mild hydrothermal treatment. Clays and Clay Minerals, 35, 271–280.
Kung, K.-H. and McBride, M.B. (1988) Electron transfer process between hydroquinone and hausmannite. Clays and Clay Minerals, 36, 297–302.
Luo, J. and Suib, S. L. (1997) Preparative parameters, magnesium effects, and anion effects in the crystallization of birnessites. Journal of Physical Chemistry B, 101, 10403–10413.
Luo, J., Huang, A., Park, S.H., Suib, S.L. and O’Young, C.-L. (1998) Crystallization of sodium-birnessite and accompanied phase transformation. Chemistry of Materials, 10, 1561–1568.
Ma, Y., Luo, J. and Suib, S.L. (1999) Syntheses of birnessites using alcohols as reducing reagents: Effects of synthesis parameters on the formation of birnessites. Chemistry of Materials, 11, 1972–1979.
Manceau, A., Gorshkov, A.I. and Drits, V.A. (1992) Structural chemistry of Mn, Fe, Co, and Ni in manganese hydrous oxides: Part I. Information from XANES spectroscopy. American Mineralogist, 77, 1133–1143.
Mandernack, K.W. and Tebo, B.M. (1993) Manganese scavenging and oxidation at hydrothermal vents and in vent plumes. Geochimica et Cosmochimica Acta, 57, 3907–3923.
McKenzie, R.M. (1971) The synthesis of birnessite, cryptomelane, and some other oxides and hydroxides of manganese. Mineralogical Magazine, 38, 493–502.
Paterson, E., Bunch, J.L. and Clark, D.R. (1986a) Cation exchange in synthetic manganates. I. Alkylammonium exchange in a synthetic phyllomanganate. Clay Minerals, 21, 949–955.
Paterson, E., Clark, D.R., Russell, J.D. and Swaffield, R. (1986b) Cation exchange in synthetic manganates. II. The structure of an alkylammonium-saturated phyllomanganate. Clay Minerals, 21, 957–964.
Post, J.E. and Veblen, D.R. (1990) Crystal structure determinations of synthetic sodium, magnesium, and potassium birnessite using TEM and the Rietveld method. American Mineralogist, 75, 477–489.
Potter, R.M. and Rossman, G.R. (1979) The tetravalent manganese oxides: Identification, hydration, and structural relationships by infrared spectroscopy. American Mineralogist. 64, 1199–1218.
Ressler, T., Brock, S.L., Wong, J. and Suib, S.L. (1999) Multiple-scattering EXAFS analysis of tetraalkylammonium manganese oxide colloids. Journal of Physical Chemistry B, 103, 6407–6420.
Silvester, E., Manceau, A. and Drits, V.A. (1997) Structure of synthetic monoclinic Na-rich birnessite and hexagonal birnessite: II. Results from chemical studies and EXAFS spectroscopy. American Mineralogist, 82, 962–978.
Uzochukwu, G.A. and Dixon, J.B. (1986) Manganese oxide minerals in nodules of two soils of Texas and Alabama. Soil Science Society of American Journal, 50, 1079–1084.
Wong, S.-T. and Cheng, S. (1992) Synthesis and characterization of pillared buserite. Inorganic Chemistry, 31, 1165–1172.
Yang, D.S. (1996) Structural properties phyllomanganates and its application to their identification in soils. Ph.D. thesis. National Taiwan University, p. 216.
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Yang, D.S., Wang, M.K. Syntheses and characterization of birnessite by oxidizing pyrochroite in alkaline conditions. Clays Clay Miner. 50, 63–69 (2002). https://doi.org/10.1346/000986002761002685
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DOI: https://doi.org/10.1346/000986002761002685