Crystal-Facet Engineering of Ferric Giniite by Using Ionic-Liquid Precursors and Their Enhanced Photocatalytic Performances under Visible-Light Irradiation

In the work presented here, well-dispersed ferric giniite microcrystals with controlled sizes and shapes are solvothermally synthesized from ionic-liquid precursors by using 1-n-butyl-3-methylimidazolium dihydrogenphosphate ([Bmim][H2PO4]) as phosphate source. The success of this synthesis relies on the concentration and composition of the ionic-liquid precursors. By adjusting the molar ratios of Fe(NO3)39H2O to [Bmim][H2PO4] as well as the composition of ionic-liquid precursors, we obtained uniform microstructures such as bipyramids exposing {111} facets, plates exposing {001} facets, hollow spheres, tetragonal hexadecahedron exposing {441} and {111} facets, and truncated bipyamids with carved {001} facets. The crystalline structure of the ferric giniite microcrystals is disclosed by various characterization techniques. It was revealed that [Bmim][H2PO4] played an important role in stabilizing the {111} facets of ferric giniite crystals, leading to the different morphologies in the presence of ionic-liquid precursors with different compositions. Furthermore, since these ferric giniite crystals were characterized by different facets, they could serve as model Fenton-like catalysts to uncover the correlation between the surface and the catalytic performance for the photodegradation of organic dyes under visible-light irradiation. Our measurements indicate that the photocatalytic activity of as-prepared Fenton-like catalysts is highly dependent on the exposed facets, and the surface area has essentially no obvious effect on the photocatalytic degradation of organic dyes in the present study. It is highly expected that these findings are useful in understanding the photocatalytic activity of Fenton-like catalysts with different morphologies, and suggest a promising new strategy for crystal-facet engineering of photocatalysts for wastewater treatment based on heterogeneous Fenton-like process.