Ligand-Dependent Colloidal Stability Controls the Growth of Aluminum Nanocrystals

Abstract

The precise size- and shape-controlled synthesis of monodisperse Al nanocrystals remains an open challenge, limiting their utility for numerous applications that would take advantage of their size and shape-dependent optical properties. Here we pursue a molecular-level understanding of the formation of Al nanocrystals by titanium(IV) isopropoxide-catalyzed decomposition of AlH₃ in Lewis base solvents. As determined by electron paramagnetic resonance spectroscopy of intermediates, the reaction begins with the formation of Ti³⁺-AlH₃ complexes. Proton nuclear magnetic resonance spectroscopy indicates isopropoxy ligands are removed from Ti by Al, producing aluminum(III) isopropoxide and low-valent Ti³⁺ catalysts. These Ti³⁺ species catalyze elimination of H₂ from AlH₃ inducing the polymerization of AlH₃ into colloidally unstable low-valent aluminum hydride clusters. These clusters coalesce and grow while expelling H₂ to form colloidally stable Al nanocrystals. The colloidal stability of the Al nanocrystals and their size is determined by the molecular structure and density of coordinating atoms in the reaction, which is controlled by choice of solvent composition.