Photosensitized Radical-Anion-Driven Metal-Free Selective Reduction of Aldehydes Using Graphene Oxide as an Electron Relay Mediator under Visible Light.

Despite the modern boost, developing a new photocatalytic system for the reduction of aldehydes is still challenging due to their high negative reduction potential. Herein, we have used a metal-free photoinduced electron-transfer system based on a cheap and readily available organic dye eosin Y (EY), graphene oxide (GO), and ammonium oxalate (AO) for photocatalytic reduction of structurally diverse aldehydes under sustainable conditions. The protocol shows remarkable selectivity for the photocatalytic reduction of aldehydes over ketones. The decisive interaction of GO and AO with the various states of EY (ground, singlet, triplet, and radical anions), which are responsible for the commencement of the reaction, was examined by various theoretical, optical, electrochemical, and photo-electrochemical studies. The synergetic system of GO, EY, and AO is appropriate for enhancing the separation efficiency of visible-light-induced charge carriers. GO nanosheets act as an electron reservoir to accept and transport photogenerated electrons from the photocatalytic system to the reactant. The reduction of the GO during the process ruled out the back transfer of photoexcited charges. Control experiments explained that the reaction involves two stages: electron transfer and protonation. This process eliminates the necessity of precious-metal-based photocatalysts or detrimental sacrificial agents and overcomes the redox potential limitations for the photoreduction of aldehydes.