We present a facile strategy for the shape-controlled synthesis of F-substituted hydroxyapatite (FHAp) microcrystals based upon using a combination of Na(2)EDTA and citric acid (CA). Novel, well-defined FHAp microcrystals of various shapes, such as hexagonal disks with predominant (0 0 0 1) faces, hexagonal shuttles, hexagonal prisms, icosahedrons, and hexagonal microrods with tunable aspect ratios, were fabricated. In particular, FHAp hollow microcrystals with tunable shapes were fabricated directly without using any additional template. The central features of our approach are the use of both Na(2)EDTA and CA as two distinct chelating reagents and the use of substitution ions (F(-)) itself as a growth inhibitor for the FHAp crystals. F(-) ions were found to play a critical role in the formation of hexagonally shaped FHAp microcrystals, and in the one-pot formation of hollow microcrystals, which relies on the addition order of F(-) ions in the synthesis.
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