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(H2O)6]2{[Co(H2O)4]4[WZn3(H2O)2(ZnW9O34)2]}·8H2O (Co6Zn5W19) is synthesized by combining [WZn3(H2O)2(ZnW9O34)2]12- (Zn5W19) 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, Co6Zn5W19 displays a high proton conductivity (3.55 × 10-4 S cm-1 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. I-V curves of a tablet of Co6Zn5W19 in the reduced and oxidized states yield conductivities of 1.26 × 10-6 and 5 × 10-8 S cm-1, respectively. Moreover, Co6Zn5W19 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.