Crystallization of Transition-Metal Oxides in Aqueous Solution beyond Ostwald Ripening

The crystallization mechanism of transition-metal oxides (TMOs) in a solution was examined based on ZnO crystallization using in-situ x-ray absorption fine structure (XAFS) measurements at the Zn K edge and semi-empirical quantum chemistry (SEQC) simulations. The XAFS results quantitatively determine the local structural and chemical properties around a zinc atom at successive stages from Zn(NO₃)₂ to ZnO in an aqueous solution. The results also show that a zinc atom in Zn(NO₃)₂ ions dissolves in a solution and bonds with approximately three oxygen atoms at room temperature (RT). When hexamethylenetetramine (C₆H₁₂N₄) is added to the solution at RT, a stable Zn-O complex consisting of six Zn(OH)₂s is formed, which is a seed of ZnO crystals. The Zn-O complexes partially and fully form into a wurtzite ZnO at 60 and 80 °C, respectively. Based on the structural properties of Zn-O complexes determined by extended-XAFS (EXAFS), SEQC simulations clarify that Zn-O complexes consecutively develop from a linear structure to a polyhedral complex structure under the assistance of hydroxyls (OH^-s) in an aqueous solution. In a solution with a sufficient concentration of OH^-s, ZnO spontaneously grows through the merging of ZnO seeds (6Zn(OH)₂s), reducing the total energy by the reactions of OH^-s. ZnO crystallization suggests that the crystal growth of TMO can only be ascribed to Ostwald ripening when it exactly corresponds to the size growth of TMO particles.