• graphene;
  • nanosheets;
  • photocatalysis;
  • hollow spheres;
  • CO2 conversion


Robust hollow spheres consisting of molecular-scale alternating titania (Ti0.91O2) nanosheets and graphene (G) nanosheets are successfully fabricated by a layer-by-layer assembly technique with polymer beads as sacrificial templates using a microwave irradiation technique to simultaneously remove the template and reduce graphene oxide into graphene. The molecular scale, 2D contact of Ti0.91O2 nanosheets and G nanosheets in the hollow spheres is distinctly different from the prevenient G-based TiO2 nanocomposites prepared by simple integration of TiO2 and G nanosheets. The nine times increase of the photocatalytic activity of G-Ti0.91O2 hollow spheres relative to commercial P25 TiO2 is confirmed with photoreduction of CO2 into renewable fuels (CO and CH4). The large enhancement in the photocatalytic activity benefits from: 1) the ultrathin nature of Ti0.91O2 nanosheets allowing charge carriers to move rapidly onto the surface to participate in the photoreduction reaction; 2) the sufficiently compact stacking of ultrathin Ti0.91O2 nanosheets with G nanosheets allowing the photogenerated electron to transfer fast from the Ti0.91O2 nanosheets to G to enhance lifetime of the charge carriers; and 3) the hollow structure potentially acting as a photon trap-well to allow the multiscattering of incident light for the enhancement of light absorption.