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Fominykh, Ksenia; Böhm, Daniel; Zhang, Siyuan; Folger, Alena; Döblinger, Markus; Bein, Thomas; Scheu, Christina; Fattakhova-Rohlfing, Dina (2017): Nonagglomerated Iron Oxyhydroxide Akaganeite Nanocrystals Incorporating Extraordinary High Amounts of Different Dopants. In: Chemistry of Materials, Vol. 29, Nr. 17: S. 7223-7233
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Dispersible nonagglomerated akaganeite (ss-FeOOH) nanocrystals doped with various elements in different oxidation states such as Co(II), Ni(II), V(III), Sn(IV), Si(IV), and Nb(V) were prepared using a microwave assisted solvothermal synthesis in tert-butanol. The doping elements could be incorporated in very high concentrations of up to 20 at.%, which is attributed to the kinetic control of the phase formation during the solvothermal reaction, together with the extremely small crystal size, which can stabilize the unusual structural compositions. The particle morphology is mostly anisotropic consisting of nanorods similar to 4 nm in width and varying length. Depending on the doping element, the length ranges from similar to 4 nm, resulting in an almost spherical shape, to 90 nm, giving the highest aspect ratio. The particles are perfectly dispersible in water, giving stable colloidal dispersions that can be deposited on different substrates to produce thin films 35-250 nm thick. In addition, films up to 30,mu m thick, consisting of interconnected mesoporous spheres, can be prepared in situ during the reactions. The nanostructures assembled from akaganeite nanocrystals are stable up to high temperatures of >400 degrees C. They can be transformed to hematite (alpha-Fe2O3) by heating between 480 degrees C and 600 degrees C without losing the morphology, which can be used for the fabrication of doped hematite nanostructures. The tunable properties of the doped akaganeite nanoparticles make them excellent candidates for a wide range of applications, as well as versatile building blocks for the fabrication of doped hematite nanomorphologies.