Large-scale synthesis of TiO2 microspheres with hierarchical nanostructure for highly efficient photodriven reduction of CO2 to CH4.

In this study, a simple and reproducible synthesis strategy was employed to fabricate TiO2 microspheres with hierarchical nanostructure. The microspheres are macroscopic in the bulk particle size (several hundreds to more than 1000 μm), but they are actually composed of P25 nanoparticles as the building units. Although it is simple in the assembly of P25 nanoparticles, the structure of the as-prepared TiO2 microspheres becomes unique because a hierarchical porosity composed of macropores, larger mesopores (ca. 12.4 nm), and smaller mesopores (ca. 2.3 nm) has been developed. The interconnected macropores and larger mesopores can be utilized as fast paths for mass transport. In addition, this hierarchical nanostructure may also contribute to some extent to the enhanced photocatalytic activity due to increased multilight reflection/scattering. Compared with the state-of-the-art photocatalyst, commercial Degussa P25 TiO2, the as-prepared TiO2 microsphere catalyst has demonstrated significant enhancement in photodriven conversion of CO2 into the end product CH4. Further enhancement in photodriven conversion of CO2 into CH4 can be easily achieved by the incorporation of metals such as Pt. The preliminary experiments with Pt loading reveal that there is still much potential for considerable improvement in TiO2 microsphere based photocatalysts. Most interestingly and significantly, the synthesis strategy is simple and large quantity of TiO2 microspheres (i.e., several hundred grams) can be easily prepared at one time in the lab, which makes large-scale industrial synthesis of TiO2 microspheres feasible and less expensive.