Structural and mineralogical variation upon reoxidation of reduced Fe-bearing clay minerals during thermal activation

The hydroxyl radicals (OH) produced from Fe(II) oxidation upon reoxidation of reduced Fe-bearing clay minerals (RFC) have received increased attention and thermal activation was used to enhance Fe(II) oxidation to improve OH production. However, changes in mineral morphology and structure during thermally-activated RFC reoxidation are not yet clear. Herein, the Fe(II) oxidation extent was measured by chemical analysis during the reoxidation of model RFC (reduced nontronite (rNAu-2) at elevated temperatures. Mineralogical variation of rNAu-2 particles was observed by scanning electron microscopy (SEM), Mössbauer spectra, and X-ray photoelectron spectroscopy (XPS). The structural Fe(II) oxidation in rNAu-2 was accelerated with increasing temperature, accompanied by the transformation of structural entities and the dissolution of Fe and Si, while the overall structure of rNAu-2 minerals was relatively intact. The surface microstructure of particles showed the dissolved holes, net-shape flocs, and even large pore channels after Fe(II) oxidation by thermal activation. Moreover, the rearrangement of structural Fe(II) entities, the regeneration of edge Fe(II), and the electron transport from the interior to the edge were enhanced during rNAu-2 reoxidation by thermal activation. The increasing electron transfer at elevated temperatures could possibly be owing to the increasing number of reactive sites by increasing the internal disorder of rNAu-2. This work provides novel insights into the structural and mineralogical changes in promoting electron transfer upon RFC reoxidation.