H-2 may be evolved biphasically using a polarised liquid|liquid interface, acting as a "proton pump", in combination with organic soluble metallocenes as electron donors. Sustainable H-2 production requires methodologies to recycle the oxidised donor. Herein, the photo-recycling of decamethylferrocenium cations (DcMFc(+)) using aqueous core-shell semiconductor CdSe@CdS nanoparticles is presented. Negative polarisation of the liquid|liquid interface is required to extract DcMFc(+) to the aqueous phase. This facilitates the efficient capture of electrons by DcMFc(+) on the surface of the photo-excited CdSe@CdS nanoparticles, with hydrophobic DcMFc subsequently partitioning back to the organic phase and resetting the system. TiO2 (P25) and CdSe semiconductor nanoparticles failed to recycle DcMFc(+) due to their lower conduction band energy levels. During photo-recycling, CdS (on CdSe) may be self-oxidised and photo-corrode, instead of water acting as the hole scavenger.