Hostname: page-component-848d4c4894-mwx4w Total loading time: 0 Render date: 2024-06-20T20:24:45.445Z Has data issue: false hasContentIssue false

Synthesis of Birnessite from the Oxidation of Mn2+ by O2 in Alkali Medium: Effects of Synthesis Conditions

Published online by Cambridge University Press:  01 January 2024

Xiong Han Feng
Affiliation:
College of Resources and Environment, Huazhong Agricultural University, Wuhan 430070, PR China
Fan Liu*
Affiliation:
College of Resources and Environment, Huazhong Agricultural University, Wuhan 430070, PR China
Wen Feng Tan
Affiliation:
College of Resources and Environment, Huazhong Agricultural University, Wuhan 430070, PR China
Xiang Wen Liu
Affiliation:
Testing Center, China University of Geosciences, Wuhan 430074, PR China
*
*E-mail address of corresponding author: liufan@mail.hzau.edu.cn

Abstract

An O2 oxidation and freeze-dry procedure has been used to synthesize birnessite through the oxidation of Mn2+ in alkali media. The effects of O2 flow rate, the fluxion velocity of reaction suspension, the reaction temperature, pretreatment the reaction solutions with N2, and the hydration conditions on the purity of birnessite, the crystallinity, the ion-exchange properties, and the phase transformation of intermediate phases were examined. Buserite with a 1 nm basal spacing, produced after the oxidation, is transformed to 0.7 nm Na birnessite by complete freeze drying. Increasing the fluxion velocity of the reaction suspension and the O2 flow rate facilitated oxidation of Mn(OH)2. Prephase I (a phase related to hausmannite, γ-Mn3O4 (Luo and Suib, 1997; Luo et al., 1998), and feitknechtite (β-MnOOH) were formed as intermediates during the synthesis. Mechanical stirring was used to change the fluxion velocity of the reactive suspension. When the speed of stirring and the O2 flow rate were raised to 250 rpm and 3.0 L/min, respectively, or 450 rpm and 2.0 L/min, respectively, birnessite was the only phase in the final product. Irrespective of temperature in other reactions, pure birnessite was synthesized as long as the temperature during the initial mixing of the reaction solutions was maintained below 10°C. Increasing the reaction temperature led to a larger crystal size, better crystallinity and lower surface area. The pretreatment of solutions with N2 or O2 had little effect on the synthesis; synthesized birnessites had the same purity (100%) as, and similar crystallinity to, that of the no-pretreatment control. Dehydration of the buserite by freeze drying and heating at 60°C did not affect the production of birnessite; however, the latter caused partial loss of ion-exchange capacity with Mg2+. The pathways of the birnessite formation in this study might be:

  1. (1) Mn(OH)2 (amorphous) → feitknechtite → buserite → birnessite, and

  2. (2) Mn(OH)2 (amorphous) → prephase I → feitknechtite → buserite → birnessite

Mn(OH)2 existed in an X-ray amorphous state, not in the form of ‘pyrochroite’, during the synthesis.

The adopted conditions for synthesis of pure birnessite were NaOH to Mn molar ratio of 13.7, O2 flow rate of 2 L/min and oxidation for 5 h during vigorous stirring at 450 rpm at room temperature. The birnessite synthesized had a hexagonal platy morphology with good crystallinity, an average composition of Na0.25MnO2.07.0.66H2O, and a surface area of 38 m2/g.

Type
Research Article
Copyright
Copyright © 2004, The Clay Minerals Society

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Bricker, O.P., (1965) Some stability relations in the system Mn-O2-H2O and one atmosphere total pressure American Mineralogist 50 12961354.Google Scholar
Brown, G., Brindley, G.W. and Brown, G., (1984) Associated minerals Crystal Structures of Clay Minerals and their X-ray Identification London Mineralogical Society 361410.Google Scholar
Buser, W. Graf, P. and Feitnecht, W., (1954) Beitrag zur Kenntnis der Mangan(II)-manganite und der–MnO2 Helvetica Chimica Acta 37 23222333 10.1002/hlca.19540370746.CrossRefGoogle Scholar
Cai, J. Liu, J. and Suib, S.L., (2002) Preparative parameters and framework dopant effects in the synthesis of layer-structure birnessite by air oxidation Chemistry of Materials 14 20712077 10.1021/cm010771h.CrossRefGoogle Scholar
Chen, X. Shen, Y.F. Suib, S.L. and O’Young, C.L., (2002) Characterization of manganese oxide octahedral molecule sieve (M-OMS-2) materials with different metal cation dopants Chemistry of Materials 14 940948 10.1021/cm000868o.CrossRefGoogle Scholar
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 883890 10.1021/ic961088d.CrossRefGoogle Scholar
Chukhrov, F.V. and Groshkov, A.I., (1981) Iron and manganese oxide minerals in soils Transactions of the Royal Society of Edinburgh 72 195200 10.1017/S0263593300009998.CrossRefGoogle Scholar
Cornell, R.M. and Giovanoli, R., (1988) Transformation of hausmannite into birnessite in alkaline media Clays and Clay Minerals 36 249257 10.1346/CCMN.1988.0360306.CrossRefGoogle Scholar
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 946961 10.2138/am-1997-9-1012.CrossRefGoogle Scholar
Drits, V.A. Lanson, B. Bougerol-Chaillout, C. Gorshkov, A.I. and Manceau, A., (2002) Structure of heavy-metal sorbed birnessite: Part 2. Results from electron diffraction American Mineralogist 87 16461661 10.2138/am-2002-11-1214.CrossRefGoogle Scholar
Duncan, M.J. Leroux, F. Corbeit, J.M. and Nazar, L.F., (1998) Todorokite as a Li insertion cathode: Comparison of a large tunnel framework ‘MnO2’ structure with its related layered structure Journal of the Electrochemical Society 145 37463757 10.1149/1.1838869.CrossRefGoogle Scholar
Feng, Q. Kanoh, H. Miyai, Y. and Ooi, K., (1995) Hydrothermal synthesis of lithium and sodium manganese oxides and their metal ion extraction/insertion reactions Chemistry of Materials 7 12261232 10.1021/cm00054a024.CrossRefGoogle Scholar
Giovanoli, R., Varentsov, I.M. and Grasselly, G., (1970) On natural and synthetic manganese nodules Geology and Geochemistry of Manganese Vol 1 Budapest Publishing House of the Hungarian Academy of Science 159202.Google Scholar
Giovanoli, R. Stähli, E. and Feitknecht, W., (1970) Über Oxidehydroxide des vierwertigen Mangans mit Schichtengitter. 1. Natriummangan (II, III)- manganat(IV) Helvetica Chimica Acta 53 209220 10.1002/hlca.19700530203.CrossRefGoogle Scholar
Giovanoli, R. Stähli, E. and Feitknecht, W., (1970) Über Oxidehydroxide des vierwertigen Mangans mit Schichtengitter. 2. Mangan(III)-manganat(IV) Helvetica Chimica Acta 53 453464 10.1002/hlca.19700530302.CrossRefGoogle Scholar
Giovanoli, R. Buhler, H. and Sokolowska, K., (1973) Synthetic lithiophorite: electron microscopy and X-ray diffraction Journal de Microscopie 18 271284.Google Scholar
Golden, D.C. Chen, C.C. and Dixon, J.B., (1986) Synthesis of todorokite Science 231 717719 10.1126/science.231.4739.717.CrossRefGoogle ScholarPubMed
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 511520 10.1346/CCMN.1986.0340503.CrossRefGoogle Scholar
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 271280 10.1346/CCMN.1987.0350404.CrossRefGoogle Scholar
Huang, P.M., Sparks, D.L. and Suarez, D.L., (1991) Kinetics of Redox reactions on manganese oxides and its impact on environmental quality Rate of Soil Chemical Processes Madison, Wisconsin, USA Soil Science Society of America 191230.Google Scholar
Jones, L.H.P. and Milne, A.A., (1956) Birnessite a new manganese oxide mineral from Aberdeenshire, Scotland Mineralogical Magazine 31 283288 10.1180/minmag.1956.031.235.01.CrossRefGoogle Scholar
Kijima, N. Yasuda, H. Sato, T. and Yoshimura, Y., (2001) Preparation and characterization of open tunnel oxide α-MnO2 precipitated by ozone oxidation Journal of Solid State Chemistry 159 94102 10.1006/jssc.2001.9136.CrossRefGoogle Scholar
Kim, J.B. Dixon, J.B. Chusuei, C.C. and Deng, Y.J., (2002) Oxidation of Chromium(III) to (VI) by Manganese Oxides Soil Science Society of America Journal 66 306315 10.2136/sssaj2002.3060.CrossRefGoogle Scholar
Lanson, B. Drits, V.A. Silvester, E. and Manceau, A., (2000) Structure of H-exchanged hexagonal birnessite and its mechanism of formation from Na-rich monoclinic buserite at low pH American Mineralogist 85 826838 10.2138/am-2000-5-625.CrossRefGoogle Scholar
Lanson, B. Drits, V.A. Gaillot, A.C. Plançon, A. and Manceau, A., (2002) Structure of heavy-metal sorbed birnessite: Part 1. Results from X-ray diffraction American Mineralogist 87 16311645 10.2138/am-2002-11-1213.CrossRefGoogle Scholar
Lanson, B. Drits, V.A. Feng, Q. and Manceau, A., (2002) Structure of synthetic birnessite: Evidence for a triclinic one-layer unit cell American Mineralogist 87 16621671 10.2138/am-2002-11-1215.CrossRefGoogle Scholar
Levinson, A.A., (1962) Birnessite from Mexico American Mineralogist 47 790791.Google Scholar
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 1040310413 10.1021/jp9720449.CrossRefGoogle Scholar
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 15611568 10.1021/cm970745c.CrossRefGoogle Scholar
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 19721979 10.1021/cm980399e.CrossRefGoogle Scholar
Mandernack, K.W. and Tebo, B.M., (1993) Manganese scavenging and oxidation at hydrothermal vents and in vent plumes Geochimica et Cosmochimica Acta 57 39073923 10.1016/0016-7037(93)90343-U.CrossRefGoogle Scholar
McBride, M.B., (1987) Adsorption and oxidation of phenolic compounds by iron and manganese oxides Journal of the American Chemical Society 51 14661472.Google Scholar
McKenzie, R.M., (1971) The synthesis of birnessite, cryptomelane, and some other oxides and hydroxides of manganese Mineralogical Magazine 38 493503 10.1180/minmag.1971.038.296.12.CrossRefGoogle Scholar
McKenzie, R.M., Dixon, J.B. and Weed, S.B., (1989) Manganese oxides and hydroxides Minerals in Soil Environments Madison, Wisconsin, USA Soil Science Society of America 439465.Google Scholar
Oscarson, D.W. Huang, P.M. Defosse, C. and Herbillon, A., (1981) The oxidative power of Mn(IV) and Fe(III) oxides with respect to As(III) in terrestrial and aquatic environments Nature 291 5051 10.1038/291050a0.CrossRefGoogle Scholar
Paterson, E. Bunch, J.L. and Clark, D.R., (1986) Cation exchange in synthetic manganates: I. Alkylammonium exchange in a synthetic phyllomanganate Clay Minerals 21 949955 10.1180/claymin.1986.021.5.08.CrossRefGoogle Scholar
Post, J.E., Skinner, H.C.W. and Fitzpatrick, R.W., (1992) Crystal structures of manganese oxide minerals Biomineralization Processes of Iron and Manganese–Modern and Ancient Environments Cremlingen, Germany CATENA Verlag 5173.Google Scholar
Post, J.E., (1999) Manganese oxide minerals: crystal structures and economic and environmental significance Proceedings of the National Academy of Sciences 96 34473454 10.1073/pnas.96.7.3447.CrossRefGoogle ScholarPubMed
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 477489.Google Scholar
Shen, Y.F. Zerger, R.P. Suib, S.L. McCurdy, L. Potter, D.I. and O’Young, C.L., (1993) Manganese oxide octahedral molecular sieves: Preparation, characterization and application Science 260 511515 10.1126/science.260.5107.511.CrossRefGoogle Scholar
Siegel, M.D. and Turner, S., (1983) Crystalline todorokite associated with biogenic debris in manganese nodules Science 219 172174 10.1126/science.219.4581.172.CrossRefGoogle ScholarPubMed
Stähli, E., (1968) Öber manganate(IV) mit Schichten-Strucktur Switzerland University of Bern PhD thesis.Google Scholar
Tu, S. Racz, G.J. and Goh, T.B., (1994) Transformations of synthetic birnessite as affected by pH and manganese concentration Clays and Clay Minerals 42 321330 10.1346/CCMN.1994.0420310.CrossRefGoogle Scholar
Violante, A. and Pigna, M., (2002) Competitive sorption of arsenate and phosphate on different clay minerals and soils Soil Science Society of America Journal 66 17881796 10.2136/sssaj2002.1788.CrossRefGoogle Scholar
Wadsley, A.D., (1950) Synthesis of some hydrated manganese minerals American Mineralogist 35 485488.Google Scholar
Wadsley, A.D., (1950) A hydrous manganese oxide with exchange properties Journal of the American Chemical Society 72 1881–1784 10.1021/ja01160a104.CrossRefGoogle Scholar
Witzemann, E.J., (1915) A new method of preparation and some interesting transformations of colloidal manganese dioxide Journal of the American Chemical Society 37 10791091 10.1021/ja02170a009.CrossRefGoogle Scholar
Witzemann, E.J., (1917) The variation in the physical properties of precipitated and colloidal manganese dioxide from the point of view of physical chemical equilibrium Journal of the American Chemical Society 39 2533 10.1021/ja02246a003.CrossRefGoogle Scholar
Yang, D.S. and Wang, M.K., (1991) Mechanism on formation of birnessite in alkali media Journal of the Chinese Agricultural Chemical Society 29 106117 (in Chinese).Google Scholar
Yang, D.S. and Wang, M.K., (2002) Syntheses and characterization of birnessite by oxidizing pyrochroite in alkaline conditions Clays and Clay Minerals 50 6369 10.1346/000986002761002685.CrossRefGoogle Scholar