A Polyoxometalate-Based Inorganic Porous Material with both Proton and Electron Conductivity by Light Actuation: Photocatalysis for Baeyer-Villiger Oxidation and Cr(VI) Reduction.

Two-dimensional (2D) crystalline porous materials with designable structures and high surface areas are currently a hot research topic in the field of proton- and electron-conducting materials, which provide great opportunities to orderly accommodate carriers in available spaces and to accurately understand the conducting path. The 2D dual-conductive inorganic framework [Co(HO)]{[Co(HO)][WZn(HO)(ZnWO)]}·8HO () is synthesized by combining [WZn(HO)(ZnWO)] () and a Co(II) ion via a hydrothermal method. Due to the presence of a consecutive H-bonding network, electrostatic interactions, and packing effects between the framework and guest molecules, displays a high proton conductivity (3.55 × 10 S cm under 98% RH and 358 K) by a synergistic effect of the combined components. Additionally, a photoactuated electron injection into the semiconducting materials is an important strategy for switching electronic conductivity, because it can efficiently reduce the frameworks without destroying the crystallinity. - curves of a tablet of in the reduced and oxidized states yield conductivities of 1.26 × 10 and 5 × 10 S cm, respectively. Moreover, is also successfully applied in the photocatalytic reduction of the toxic Cr(VI) metal ion by utilizing its excellent electronic storage capacity and Baeyer-Villiger (BV) oxidation in a molecular oxygen/aldehyde system.