Determination and quantification of the local environments in stoichiometric and defect jarosite by solid-state 2H NMR spectroscopy

The nature and concentrations of the local environments in a series of deuterated jarosite (nominally AFe(3)(SO4)(2)(OD)(6) with A = K, Na, and D3O) samples with different levels of iron and cation vacancies have been determined by H-2 MAS NMR spectroscopy at ambient temperatures. Three different local deuteron environments, Fe2OD, FeOD2, and D2O/D3O+, can be separated based on their very different Fermi contact shifts of delta approximate to 237, 70, and 0 ppm, respectively. The FeOD2 group arises from the charge, compensation of the Fe3+ vacancies, allowing the concentrations of the vacancies to be readily determined. Analysis of the 2 H quadrupole interaction indicates that the FeOD2 groups are mobile, undergoing rapid 180 degrees flips on the NMR time scale; the D2O/D3O+ species (located on the A sites) undergo close to isotropic motion, whereas the Fe20D groups are rigid and are hydrogen-bonded to nearby sulfate 0 atoms, with a (Fe)OD-O(S) distance of 2.79(4) angstrom. No evidence for the intrinsic protonation reaction Fe2OH + H3O+ -> Fe2OH2 + H2O is found in the hydronium jarosite, suggesting that this mechanism is not the cause of the anomalous magnetic behavior of this material. The results illustrate that 2 H MAS NMR spectroscopy is an excellent probe of the local environments and defects, on the atomic/molecular level, providing information that is complementary to diffraction techniques and that will help to rationalize the magnetic properties of these materials.