Understanding Wavelength-Dependent Synergies between Morphology and Photonic Design in TiO₂-Based Solar Powered Redox...

Solar powered redox cells (SPRCs) are promising for large-scale and long-term storage of solar-energy, particularly when coupled with redox flow batteries (RFBs). While efforts have primarily focused on heterostructure engineering, the potential of synergistic morphology and photonic design has not been carefully studied. Here, we investigate the wavelength-dependent effects of light-absorption and charge transfer characteristics on the performance of gold decorated TiO₂-based SPRC photoanodes operating with RFB-compatible redox couples. Through an in-depth optical and photoelectrochemical characterization of three complementary TiO₂ microstructures, namely nanotubes, honeycombs, and nanoparticles, we elucidate the combined effects of nanometer-scale semiconductor morphology and plasmonic design across the visible spectrum. In particular, thin-walled TiO₂ nanotubes exhibit a ∼ 50% increase in solar-to-chemical efficiency (STC) compared to thick-walled TiO₂ honeycombs thanks to improved charge transfer. Au nanoparticles both increase generation and interfacial charge transfer (above bandgap) and promote hot carrier injection (below bandgap) leading to a further 25% increase in STC. Overall, Au/TiO₂ nanotubes achieve a high photocurrent at 0.098 mA/cm² and an excellent STC of 0.06%, among the highest with respect to the theoretical limit. The incident photon to current efficiency and internal quantum efficiency are also superior to those of bare TiO₂ showing maximum values of 54.7% and 67%, respectively. Overall, nanophotonic engineering that synergistically combines morphology optimization and plasmonic sensitization schemes offer new avenues for improving rechargeable solar-energy technologies such as solar redox flow batteries.