Capture, store and discharge. Shuttling photogenerated electrons across TiO2-silver interface

UV irradiation of TiO2 nanoparticles in the presence of Ag+ ions results in the quantitative reduction and deposition of silver on its surface. Continued UV irradiation following the deposition of Ag on the TiO2 surface causes a blue shift in the surface plasmon peak from 430 to 415 nm as these particles become charged with excess electrons. Under UV irradiation, both the charging and discharging of electrons occur at different rates, thus allowing the system to attain a steady state. Upon stopping the UV irradiation, a fraction of these electrons remain stored. The electron storage is dependent on the amount of Ag deposited on TiO2 nanoparticles with maximum capacity seen at 8.6 μM of Ag in a suspension containing 5.8 mM of TiO2. Such electron charging and discharging processes in semiconductor–metal composites need to be taken into account while evaluating the plasmon resonance induced effects in photocatalysis and photoelectrochemistry.