Sustainable green hydrogen production and value-added products through earth-abundant semiconductor-sensitized TiO 2 via PEC water splitting Oshnik Maurya, Archana Kalekar Department of Physics, Institute of Chemical Technology, Mumbai, 400019, India The transition to a low-carbon energy economy has intensified interest in photoelectrochemical (PEC) water splitting for sustainable green hydrogen production. However, widespread deployment is limited by the high cost and performance constraints of current photoelectrode materials. Titanium dioxide (TiO 2 ) remains a benchmark photoanode due to its chemical stability and abundance, but its wide bandgap restricts light absorption to the ultraviolet region, reducing overall PEC efficiency. To address this, we investigated the sensitization of TiO 2 with earth-abundant, visible-light-active semiconductors such as bismuth chalcogenides and kesterites. These materials extend light absorption into the visible region and promote efficient charge separation due to favorable band alignment. The resulting composites were characterized using XRD, SEM, UV-Vis, and PL techniques, confirming improved light harvesting and reduced electron-hole recombination. Electrochemical analyses revealed enhanced photocurrent, better charge transfer kinetics, and improved long-term stability under simulated solar conditions. In addition to water oxidation, the sluggish oxygen evolution reaction (OER) step was leveraged for value-added chemical production by introducing glycerol as a sacrificial agent. The modified TiO 2 films showed effective PEC activity toward glycerol oxidation, generating different value added products.This dual-functional approach not only boosts system efficiency but also improves economic feasibility. A framework for integrating these materials into scalable PEC devices is proposed, offering a promising pathway for low-cost hydrogen production coupled with chemical valorization. The study contributes valuable insights into the design of multifunctional, earth- abundant materials for next-generation PEC systems.
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