[EXAFS studies on adsorption-desorption mechanism of Zn at the manganite-water interface]

Microscopic structures of Zn(II) surface complexes adsorbed at the manganite(gamma-MnOOH)-water interface were studied using extended X-ray absorption fine structure(EXAFS) spectroscopy. Quantitative analysis of the EXAFS spectra showed that, in a 0.1 mol/L NaNO3 solution of pH 7.5, Zn(II) was adsorbed onto the solid surface by sharing the oxygen atom in the hydrous Zn2+ ions and in the structural unit MnO6 on the manganite surface. Most of the adsorbed Zn(II) was in the form of octahedral Zn(H2O2)(6)2+, but part of Zn(II) was adsorbed as tetrahedral Zn(OH)2 or Zn(OH)(4)2-. The average Zn-O bond length was 1.998 +/- 0.010 A (n = 3). The ZnO polyhedron of the hydrous Zn2+ ions was linked to the octahedron MnO6 of the manganite in two modes by sharing two O atoms on the edges of the polyhedral and/or one O atom on the corners of the polyhedral. EXAFS analysis of the second sphere indicated that Zn (II) adsorbed on the manganite resulted in two Zn-Mn atomic distances of 3.08 +/- 0.024A (n = 3) (R1) and 3.54 +/- 0.018 A (n = 3) (R2), corresponding to the edge-linkage (stronger adsorption site) and corner-linkage (weaker adsorption site), respectively. This result confirmed the basic hypothesis of Metastable Equilibrium Adsorption (MEA) theory from a molecular level that adsorption density gamma (mol/m2) is not a state variable, because adsorption density for the same adsorbate may have different chemical potential values due to different microscopic structure and adsorbate energy status. Macroscopic adsorption-desorption experiments showed that adsorption of Zn(II) onto manganite was largely irreversible (big adsorption hysteresis). EXAFS results indicated that the microscopic mechanism for the adsorption irreversibility was corresponded to the strong adsorption sites of edge sharing linkage between the adsorbate and adsorbent polyhedra.