Manganese oxide, adsorption

In addition to effects on the concentration of anions, the redox potential can affect the oxidation state and solubility of the metal ion directly. The most important examples of this are the dissolution of iron and manganese under reducing conditions. The oxidized forms of these elements (Fe(III) and Mn(IV)) form very insoluble oxides and hydroxides, while the reduced forms (Fe(II) and Mn(II)) are orders of magnitude more soluble (in the absence of S( — II)). The oxidation or reduction of the metals, which can occur fairly rapidly at oxic-anoxic interfaces, has an important "domino" effect on the distribution of many other metals in the system due to the importance of iron and manganese oxides in adsorption reactions. In an interesting example of this, it has been suggested that arsenate accumulates in the upper, oxidized layers of some sediments by diffusion of As(III), Fe(II), and Mn(II) from the deeper, reduced zones. In the aerobic zone, the cations are oxidized by oxygen, and precipitate. The solids can then oxidize, as As(III) to As(V), which is subsequently immobilized by sorption onto other Fe or Mn oxyhydroxide particles (Takamatsu et al, 1985). 

Adsorption and coprecipitation by hydrous iron and manganese oxides... 

Luo, J., Zhang, Q., Garcia-Martinez, J. and Suib, S.L. (2008) Adsorptive and acidic properties, reversible lattice oxygen evolution, and catalytic mechanism of cryptomelane-type manganese oxides as oxidation catalysts. Journal of the American Chemical Society, 130, 3198-3207. 

Hu, B., Chen, C., Frueh, S.J., Jin, L., Joesten, R. and Suib, S.L. (2010) Removal of aqueous phenol by adsorption and oxidation with doped hydrophobic cryptomelane-type manganese oxide (K-OMS-2) nanofibers. Journal of Physical Chemistry C, 114, 9835-9844. 

Shuman L.M. Effect of removal of organic matter and iron or manganese-oxides on zinc adsorption by soil. Soil Sci 1988 146 248-254. 

The shift of the amide I mode (FTIR spectra) from 1657 to 1646 cm-1 was attributed to a change in the a-helix native structure to fl-sheets, secondary structure conformations. Atomic Force Microscopy (AFM) images display the coating of the manganese oxide surface as well as the unfolding in a ellipsoidal chain of the protein molecules after adsorption and immobilization on the surface. 

Y. Lvov, B. Munge, O. Giraldo, I. Ichinose, S.L. Suib, and J.F. Rusling, Films of manganese oxide nanoparticles with polycations or myoglobin from alternate-layer adsorption. Langmuir 16, 8850-8857 (2000). 

Morales F., de Smit E., de Groot F.M.F., Visser T., and Weckhuysen B.M. 2007. Effects of manganese oxide promoter on the CO and H2 adsorption properties of titania-supported cobalt Fischer-Tropsch catalysts. J. Catal. 246 91-99. 

Leaching and desorption of As from its associated mineral surfaces such as iron, aluminum and manganese oxides under the influence of the aquifer complex geochemistry, largely take part in its transport from sediment to aquifer pore-water. Adsorption has widely been considered as the retardation of As transport (Smedley 2003). 

Several reactions between constituents in As-contaminated groundwater and oxic sediments controlled As mobility in the laboratory experiments. Adsorption was the primary mechanism for removing As from solution. The adsorption capacity of the oxic sediments was a function of the concentration and oxidation state of As, and the concentration of other solutes that competed for adsorption sites. Although As(lll) was the dominant oxidation state in contaminated groundwater, data from the laboratory experiments showed that As(lll) was oxidized to As(V) by manganese oxide minerals that are present in the oxic sediment. Phosphate in contaminated groundwater caused a substantial decrease in As(V) adsorption. Silica, bicarbonate and pH caused only a small decrease in As adsorption. 

Lion, L. W., Altmann, R. S. and Leckie, J. O. (1982). Trace-metal adsorption characteristics of estuarine particulate matter evaluation of contributions of iron/ manganese oxide and organic surface coatings, Environ. Sci. Technol., 16, 660-666. 

Adsorption may influence precipitation by means other than the processes mentioned above. Davies (Chapter 23) discusses the role of the surface as a catalyst for oxidation of adsorbed Mnz+. Redox reactions may contribute substantially to the formation of manganese oxide coatings on mineral surfaces in soils and sediments. 

With XPS it is possible to obtain good analytical information on the amount of metal adsorbed and, in favourable cases, to identify the chemical form of that metal. Oxidation states are readily determined and it can be shown, for example, that adsorption of Co(II) on manganese oxides results in oxidation to Co(III) (38,39), whereas adsorption of Co(II) on zirconia and alumina leads to the formation of cobalt(II) hydroxide (40). With Y-type zeolites hexaaquacobalt(II) is adsorbed as Co(II), and cobalt(III) hexaammlne is adsorbed as Co(III). The XPS spectrum of Co(II) adsorbed on chlorite was consistent with the presence of the hexaaquacobalt(II) ion for pH 3-7 and indicated that no cobalt(II) hydroxide was present (41). With kaollnlte and llllte, Co is adsorbed as Co(II) over the pH range 3-10 (39,42), it being bound as the aqua ion below pH 6 and as the hydroxide above pH 8. Measurements involving Pb have... 

The most direct evidence for surface precursor complex formation prior to electron transfer comes from a study of photoreduc-tive dissolution of iron oxide particles by citrate (37). Citrate adsorbs to iron oxide surface sites under dark conditions, but reduces surface sites at an appreciable rate only under illumination. Thus, citrate surface coverage can be measured in the dark, then correlated with rates of reductive dissolution under illumination. Results show that initial dissolution rates are directly related to the amount of surface bound citrate (37). Adsorption of calcium and phosphate has been found to inhibit reductive dissolution of manganese oxide by hydroquinone (33). The most likely explanation is that adsorbed calcium or phosphate molecules block inner-sphere complex formation between metal oxide surface sites and hydroquinone. 

Barling J, Anbar AD (2004) Molybdenum isotope fractionation during adsorption by manganese oxides. Earth Planet Sci Lett 217 315-329... 

Aveston J, Anacker EW, Johnson JS (1964) Hydrolysis of molybdenum (VI). Ultracentrifugation, acidity measurements, and Raman spectra of polymolybdates. Inorg Chem 3 735-746 Baes Jr. CF, Mesmer RE (1986) The Hydrolysis of Cations. Krieger Publishing Company, Melbourne, EL Barling J, Anbar AD (2004) Molybdenum isotope fractionation during adsorption by manganese oxides. Earth Planet Sci Lett, in press... 

---