Crystal growth. Aqueous formation and manipulation of the iron-oxo Keggin ion

There is emerging evidence that growth of synthetic and natural phases occurs by the aggregation of prenucleation clusters, rather than classical atom-by-atom growth. Ferrihydrite, an iron oxyhydroxide mineral, is the common form of Fe(3+) in soils and is also in the ferritin protein. We isolated a 10 angstrom discrete iron-oxo cluster (known as the Keggin ion, Fe13) that has the same structural features as ferrihydrite. The stabilization and manipulation of this highly reactive polyanion in water is controlled exclusively by its counterions. Upon dissolution of Fe13 in water with precipitation of its protecting Bi(3+)-counterions, it rapidly aggregates to ~22 angstrom spherical ferrihydrite nanoparticles. Fe13 may therefore also be a prenucleation cluster for ferrihydrite formation in natural systems, including by microbial and cellular processes.