Crystallization of 2D TiO 2 Nanosheets via Oriented Attachment of 1D Coordination Polymer.

Demystifying the molecular mechanism of growth is vital for the rational design, synthesis, and optimization of functional nanomaterials. Despite the promising perspectives and extensive efforts, the growth mechanism of atomically thin TiO ₂ (B) nanosheets remains unclear, hence it is difficult to tune their band and surface structures. Herein, we report an oriented attachment-based crystallization mechanism of TiO ₂ (B) nanosheets from a 1D titanium glycolate coordination polymer through hydrolysis and condensation. With time-tracking experiments, this 1D coordination polymer is found to be an intermediate in the synthesis of TiO ₂ (B) nanosheets by using Ti alkoxides and chlorides as precursors, suggesting the universality of the 1D-to-2D growth mechanism. Such a side-to-side attachment pathway bridges the classical and nonclassical interpretations of crystallization, and meanwhile hints at the possibility of other 1D complexes as potential precursors for 2D materials.