Crystal structure of Ni-sorbed synthetic vernadite: a powder X-ray diffraction study

Vernadite is a nanocrystalline turbostratic phyllomanganate containing Ni, and is widespread in surface environments and oceanic sediments. To improve our understanding of Ni uptake in this mineral, two series of analogues of vernadite (δ-MnO2) were prepared with Ni/Mn atomic ratios of 0.002-0.105 at pH4 and 0.002-0.177 at pH 7. Their structures were characterized using X-ray powder diffraction (XRD). The δ-MnO2 nano-crystals are essentially monolayers with coherent scattering domains sizes of ∼10 A perpendicular to the layering and ∼55 A within the layer plane. For Ni/Mn < 0.01, the layer charge deficit is apparently balanced entirely by interlayer Mn, Na and protons. At higher Ni/Mn, Ni occupies the same site as interlayer Mn above and below vacant sites within the MnO2 layer and at sites along the edges of the layer. However, the layer charge is balanced differently at the two pH values. At pH 4, Ni uptake is accompanied by a reduction in structural Na and protons, whereas interlayer Mn remains strongly bound to the layers. At pH 7, interlayer Mn is less strongly bound and is partially replaced by Ni. The results of this study also suggest that the number of vacant octahedral sites and multi-valent charge-copmpensating interlayer species are underestimated by the currently used structure models of δ-MnO2.