Zeolitic intralayer microchannels of magadiite, a natural layered silicate, to boost green organic synthesis.

Despite the considerable attention given to the applications of magadiite in previous research, the properties of this natural layered silicate have remained mysterious due to the lack of crystal structure information. On the other hand, no one has doubted the intercalation capability between the layers. Here we succeed in determining the structure of magadiite using X-ray pair distribution functions and synchrotron powder diffractometry. We discover unexpected zeolitic microchannels within the layers. We describe efficient synthesis of 100% pure benzoic acid from toluene by using magadiite as an additive in a TiO2 photocatalytic system oxidizing toluene. Based on the uncovered structure of magadiite, we clarify the mechanism of this unique photocatalytic system: the microchannels of magadiite not only separate/accommodate the desired partially oxidized product formed on TiO2 but also prevent the accumulation of the overoxidized products on the TiO2 surface that deactivates the photocatalytic activity.