Fluorinated semiconductor photocatalysts: tunable synthesis and unique properties

Semiconductor photocatalysts are of great significance in solar energy conversion and environmental remediation. To overcome serious drawbacks of these materials with respect to narrow light-response range and low quantum efficiency, a variety of strategies have been developed in the past decades to enhance the light harvesting and excitation as well as the charge transfer against recombination. In particular, fluorination of semiconductor photocatalysts can be employed to modify their surface and bulk properties, and consequently, to enhance their photocatalytic performance. This review presents a comprehensive description of the F-mediated synthesis and unique properties of fluorinated semiconductor photocatalysts, in particular titanium dioxide (TiO(2)). The available strategies for the synthesis of fluorinated photocatalysts include post-synthesis fluorination and in-situ fluorination. Depending on the synthesis route and conditions, it is possible to control the chemical nature of incorporated fluorine (such as adsorbed fluoride and lattice-doped fluorine) and the fluoride-mediated crystal modification and organization, which often results in exceptional surface and bulk physicochemical properties, giving rise to unique photocatalytic properties. Significantly, the surface fluorination induces unusual adsorption behavior and interfacial charge transfer dynamics, directly affecting photocatalytic redox properties of the surface-fluorinated photocatalysts. The lattice fluorine-doping, sole or cooperative with other complementary co-dopants, introduces special localized electronic structures and surface defect states, accounting for the exceptional visible-light photoactivity of the fluorine-doped photocatalysts. Finally, recent advances in the synthesis and properties of fluorinated photocatalysts are summarized along with perspectives on further developments in this area of research.