Water‐Soluble Organic Dyes as Molecular Photocatalysts for H2O2 Evolution

Abstract Photochemical generation of hydrogen peroxide via oxygen reduction is a critical component of emerging sustainable energy conversion concepts. Light‐absorbing semiconductors as well as electrodes modified with sensitizers typically catalyze oxygen photoreduction to hydrogen peroxide. Here, it is reported that, in contrast to these heterogeneous systems, a homogeneous solution of a metal‐free organic dye can perform the whole catalytic cycle of hydrogen peroxide photoevolution itself. This cycle can proceed with simultaneous oxidation of various organic molecules as electron donors, or even water. In the three water‐soluble dyes that are experimented with, photoevolution of peroxide occurs favorably at neutral to basic pH. The reaction is first order with respect to dye concentration, and evidence implicates a single‐electron reduction pathway with superoxide as an intermediate. Photostability of the dyes over time correlates with increased oxidation potential of the molecule. The finding that hydrogen peroxide can be produced in aqueous solution with single fully organic molecules performing the entire photocatalytic cycle creates a new avenue for the peroxide carbon free energy cycle.