Why Does Bi₂WO₆ Visible-Light Photocatalyst Always Form as Nanoplatelets?

Bi₂WO₆ nanocrystals exhibit excellent photocatalytic properties in the visible range of the solar spectrum, and intense efforts are directed at designing effective synthesis processes with control of size, morphology, and hierarchical structure. All known hydrothermal syntheses produce either nanoplatelet morphology or hierarchical structures based on such primary entities. Here we investigate the nucleation and growth of Bi₂WO₆ nanocrystals under hydrothermal conditions using in situ X-ray total scattering (TS) and powder X-ray diffraction (PXRD) measurements. It is shown that the preferential growth of Bi₂WO₆ nanoplates is due to the presence of disordered layers of Bi₂O₂²⁺ molecular complexes in the precursor solution with an approximate length of 13 Å. These layers interact with tetrahedral WO₄^2– molecular units and eventually form the disordered cubic (Bi_0.933W_0.067)­O_1.6) crystalline phase. When enough tungsten units are intertwined between Bi₂O₂²⁺ layers formation of Bi₂WO₆ pristine nanoplates takes place by necessary sideways addition of units in the ac plane. The experimentally observed formation mechanism suggests that the Bi/W atomic ratio must play a central role in the nucleation (assembly of initial crystal layers). Indeed, it is observed in separate continuous flow supercritical synthesis that for a stoichiometric (Bi/W = 2:1) precursor, a (Bi_0.933W_0.067)­O_1.6) impurity phase is always observed together with the main Bi₂WO₆ product. Excess tungsten is required in the precursor to form phase-pure Bi₂WO₆ material. Thus, the present study also reports a fast, scalable, and green method for production of this highly attractive photocatalyst.