Synthesis of Ordered Mesoporous Fe₃O₄ and γ-Fe₂O₃ with Crystalline Walls using Post-template Reduction/Oxidation

Ordered mesoporous Fe3O4 with crystalline walls (inverse spinel structure) has been synthesized for the first time, representing to the best of our knowledge, the first synthesis of a reduced mesoporous iron oxide. Synthesis was achieved by reducing ordered mesoporous alpha-Fe2O3 (corundum structure) to Fe3O4 spinel then to gamma-Fe2O3 by oxidation, while preserving the ordered mesostructure and crystalline walls throughout. Such solid/solid transformations demonstrate the stability of the mesostructure to structural phase transitions from the hexagonal close packed oxide subarray of alpha-Fe2O3 (corundum structure) to the cubic close packed subarray of Fe3O4 spinel and gamma-Fe2O3. Preliminary magnetic measurements reveal that the spins in both Fe3O4 and gamma-Fe2O3 are frozen at 295 K, despite the wall thickness (7 nm) being less than the lower limit for such freezing in corresponding nanoparticles (> 8 nm).