Effect of structural iron on nanoscroll formation via exfoliation of a high iron-content kaolin

Abstract

Nanoscroll formation by casacade intercalation–exfoliation method was investigated for a high iron-content kaolin and after the removal of its iron-bearing mineral constituents (goethite, hematite) by 11 M HCl treatment. Hindered kaolinite nanoscroll formation was observed by TEM in both cases, where the 11 M HCl treatment only slightly improved the occurrence of nanoscrolled shapes. The presence of minor amounts of well-dispersed, resilient Fe was observed after the exfoliation of 11 M HCl-treated sample, which was identified as structural Fe3+/Fe2+ in the octahedral sheet of kaolinite by Mössbauer and X-ray absorption spectroscopy. Iron substitution in the nanokaolinite TO layers was probed by computational chemistry. The computational results indicate inner coordination changes and elongation of bonds in the iron-substituted TO structure, and the increased curvature values offer an explanation for the observed experimental results for hindered nanoscroll formation. Graphical abstract: [Figure not available: see fulltext.]