Controllable Synthesis and Crystallization of Nanoporous TiO₂ Deep-Submicrospheres and Nanospheres via an Organic...

Although considerable progress has been achieved in the preparation of uniform hydrous TiO₂ spheres (HTS) through the sol-gel process, there is plenty of room left in tailoring the size and morphology of HTS on the deep-submicron scale or even nanoscale since the diameters of the so far reported HTS are mostly on the (sub)micron scale (0.3-1.2 μm). Here, we develop a novel titanium tetraisopropoxide (TTIP)-organic acid (OA)-acetonitrile (ACN)-methanol (MeOH)-H₂O system, which facilitates the control of nanoporous HTS to the range of 50-300 nm. The synthetic parameters including OA, (co-)solvent, concentration of precursor, and reaction temperature are comprehensively optimized, aiming at reproducible preparation and precise size control. Among the various OAs, n-valeric acid presents the best capability in controlling the spherical morphology and size uniformity. The synthesized amorphous HTS containing numerous micropores and mesopores show excellent hydrothermal stability and offer suitable self-template for the subsequent synthesis of mesoporous anatase TiO₂ spheres (MAT) with a large surface area of 99.1 m²/g. The obtained TiO₂ deep-submicrospheres and nanospheres with tunable sizes show great potential in various research fields.