Visible-light-driven CO₂ reduction on dye-sensitized NiO photocathodes decorated with palladium nanoparticles

The thin-layer-stacked dye-sensitized NiO photocathodes decorated with palladium nanoparticles (nPd) can be used for the visible-light-driven selective reduction of CO₂, mostly to CO, at potentials starting as low as 0 V vs. RHE (compared to -0.6 V in the dark for electrocatalysis). The photosensitization of NiO by the organic dye P1, with a surface coverage of 1.5 × 10^-8 mol cm^-2, allows the hybrid material to absorb light in the 400-650 nm range. In addition, it improves the stability and the catalytic activity of the final material decorated with palladium nanoparticles (nPd). The resulting multi-layered-type photocathode operates according to the electron-transfer-cascade mechanism. On the one hand, the photosensitizer P1 plays a central role as it generates excited-state electrons and transfers them to nPd, thus producing the catalytically active hydride material PdH . On the other hand, the dispersed nPd, absorb/adsorb hydrogen and accumulate electrons, thus easing the reductive electrocatalysis process by further driving the separation of charges at the photoelectrochemical interface. Surface analysis, morphology, and roughness have been assessed using SEM, EDS, and AFM imaging. Both conventional electrochemical and photoelectrochemical experiments have been performed to confirm the catalytic activity of hybrid photocathodes toward the CO₂ reduction. The recorded cathodic photocurrents have been found to be dependent on the loading of Pd nanoparticles. A sufficient amount of loaded catalyst facilitates the electron transfer cascade, making the amount of dye grafted at the surface of the electrode the limiting parameter in catalysis. The formation of CO as the main reaction product is postulated, though the formation of traces of other small organic molecules (e.g. methanol) cannot be excluded.