Proceedings of 13th Conference on Hybrid and Organic Photovoltaics (HOPV21)
Publication date: 11th May 2021
Photoelectrochemical (PEC) cells utilizing dye-sensitized electrodes are promising candidates for generating solar fuels using only water as a chemical feedstock.[1] Dye-sensitized photoelectrochemical (DS-PEC) systems build on knowledge gained from dye-sensitized solar cells (DSSCs). Using such an approach for proton reduction to H2 or CO2 reduction at the photocathode has a number of advantages over homogeneous systems in solution while still taking advantage of the best performing molecular photocatalysts. Charge-transfer kinetics and energetics at the catalyst-semiconductor interface are readily optimised through design of the molecular catalyst/sensitizer. PEC systems dispense with the need for a sacrificial electron donor in the water oxidation process[2] by introducing an external bias from a solar cell or by addition of a sensitized counter electrode, in a tandem device, for overall water-splitting.[3]
In the present study we interrogate recent results for DS-PEC systems utilizing novel Ruthenium-Rhenium molecular photocatalysts deposited on mesoporous NiO films for CO2 reduction, building on previous efforts from water-splitting studies. Particular interest is taken in optimizing experimental conditions, dye adsorptivity, and stability during extended periods of irradiation. Transient absorption spectroscopy is used to comment on the longevity of the charge separated state. Electrochemical measurements and gas chromatography are used to measure PEC device performance and X-ray photoelectron spectroscopy is used to monitor chemical changes on the semiconductor surface. It is apparent that more work is needed to develop efficient PEC systems by engineering longer-lived charge separated excited states on the semiconductor surface.