Nanoporous oxide films composed of nanocrystal assemblies with an aligned crystallographic orientation are key nanostructures for efficient interfacial reactions. However, a simple, template-free method for their formation remains a challenge. Layered metal hydroxide (LMH) films are a promising precursor for spontaneous formation of nanoporous oxide films.[1-4] LMHs have a layered structure comprising 2D sheets of edge-shared octahedral hydroxide, i.e., brucite structure, with or without interlayer anions and water molecules. Calcination of LMH results in dehydration, anion elimination, and volume shrinkage, leading to the spontaneous formation of nanoporous oxides.In this study, we have prepared nanoporous and ferrimagnetic magnetite (Fe3O4) films by using layered iron hydroxides, namely, green rust (GR), as a precursor. Generally, GR has a brucite-type structure containing Fe2+ and Fe3+ ions, and is highly susceptible to oxidation by oxygen in water and air, leading to the formation of iron oxyhydroxides (FeOOH). Here, GR films were electrochemically deposited on FTO substrates in an aqueous solution containing Fe2+ and NO3 − ions at room temperature. Drying the GR films in air resulted in the formation of two-type FeOOH films, depending on the electrodeposition condition. Characterization using X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, and FT-IR spectroscopy revealed that one is [010]-oriented γ-FeOOH films, and the other is [001]-oriented δ-FeOOH films. The obtained FeOOH films had a mille-feuille like morphology with 500–700 nm thickness. Heat treatment of these two-type FeOOH films under vacuum at 500 °C resulted in the formation of [110]- and [111]-oriented nanoporous Fe3O4 films. The obtained Fe3O4 films showed a ferrimagnetic behavior in VSM measurements and had a nanoporous structure comprising nanoparticles with 50–100 nm diameter.Finally, a possilble interpretation for the observed orientation relationships between the FeOOH and Fe3O4 was also discussed on the basis of pyrolysis intermediates of FeOOH and similarity in their atomic arrangements. References T. Shinagawa, M. Watanabe, T. Mori, J.-i. Tani, M. Chigane and M. Izaki, Inorg. Chem., 57, 13137 (2018).T. Shinagawa, M. Chigane and M. Izaki, ACS Omega, 6, 2312 (2021).T. Shinagawa, M. Chigane and M. Takahashi, Cryst. Growth Des., 22, 4122 (2022).T. Shinagawa, N. Kotobuki and A. Ohtaka, Nanoscale Adv., 5, 96 (2023). Figure 1
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