Phase-Migrating Z-Scheme Charge Transportation Enables Photoredox Catalysis Harnessing Water as an Electron Source

Z-schematic photocatalytic reactions are of considerable interest because of their potential for application to reductive molecular conversions to value-added chemicals using water as an electron source. However, most demonstrations of Z-scheme photocatalysis have been limited to overall water splitting. In particular, it has been basically impossible to couple the reduction of "water-insoluble compounds" with water oxidation by conventional Z-scheme systems in aqueous solution. In this work, an unconventional Z-scheme electron transportation system with a "phase-migrating" redox mediator is constructed that enables photocatalytic conversion of water-insoluble compounds by using water as an electron/proton source. In a dichloroethane (DCE)/water biphasic solution, a molecular Ir(III) complex acts as a photoredox catalyst for the reductive coupling of benzyl bromide by using ferrocene (Fc) as an electron donor in the DCE phase. On the other side, an aqueous dispersion of a Bi₄TaO₈Cl semiconductor loaded with a (Fe,Ru)O_<i>x</i> cocatalyst photocatalyzed water oxidation using ferrocenium (Fc⁺) as an electron acceptor. Because the partition coefficients of Fc⁺/Fc are significantly different, the Fc⁺ and Fc generated by photoinduced electron transfer in each reaction could be selectively extracted to the opposite liquid phase. Spontaneous phase migration enables direction-selective electron transport across the organic/water interface that connects the reduction and oxidation reactions in the separated reaction phase. Eventually, photocatalytic reductive conversion of "water-insoluble" organic compounds using "water as the electron/proton source" was demonstrated through the step-by-step Z-scheme photocatalysis with the phase-migrating Fc⁺/Fc electron transportation.