Water Vapor Photoelectrolysis in a Solid-State Photoelectrochemical Cell with TiO₂ Nanotubes Loaded with CdS and CdSe Nanoparticles

In this study, polyol-made CdS and CdSe crystalline nanoparticles (NPs) are loaded by impregnation on TiO₂ nanotube arrays (TNTAs) for solar-simulated light-driven photoelectrochemical (PEC) water vapor splitting. For the first time, we introduce a safe way to utilize toxic, yet efficient photocatalysts by integration in solid-state PEC (SSPEC) cells. The enabling features of SSPEC cells are the surface protonic conduction mechanism on TiO₂ and the use of polymeric electrolytes, such as Nafion instead of liquid ones, for operation with gaseous reactants, like water vapor from ambient humidity. Herein, we studied the effects of both the operating conditions in gaseous ambient atmospheres and the surface modifications of TNTAs-based photoanodes with well-crystallized CdS and CdSe NPs. We showed 3.6 and 2.5 times increase in the photocurrent density of defective TNTAs modified with CdS and CdSe, respectively, compared to the pristine TNTAs. Electrochemical impedance spectroscopy and structural characterizations attributed the improved performance to the higher conductivity induced by intrinsic defects as well as to the enhanced electron/hole separation at the TiO₂/CdS heterojunction under gaseous operating conditions. The SSPEC cells were evaluated by cycling between high relative humidity (RH) (80%) and low RH levels (40%), providing direct evidence of the effect of RH and, in turn, adsorbed water, on the cell performance. Online mass spectrometry indicated the corresponding difference in the H₂ production rate. In addition, a complete restoration of the SSPEC cell performance from low to high RH levels was also achieved. The presented system can be employed in off-grid, water depleted, and air-polluted areas for the production of hydrogen from renewable energy and provides a solution for the safe use of toxic, yet efficient photocatalysts.