Synthesis Control of Charge Separation at Anatase TiO₂ Thin Films Studied by Transient Surface Photovoltage Spectroscopy

For the efficient photocatalytic oxidation of organic pollutants at surfaces of semiconductors, photogenerated holes shall be separated toward the surface and transferred to reactive surface sites, whereas the transfer of photogenerated electrons toward the surface shall be minimized. In this Research Article, the identification of suitable synthesis control of charge separation combined with an in-depth understanding of charge kinetics and trapping passivation mechanisms at the related surfaces can provide tremendous opportunities for boosting the photocatalytic performance. In this work, a comprehensive transient surface photovoltage spectroscopy study of charge separation at anatase TiO2 thin films, synthesized by ultrasonic spray pyrolysis from titanium(IV) isopropoxide (TTIP)–acetylacetone (AcacH) based precursor is reported. By varying the amount of AcacH in the precursor solution, an experimental approach of synthesis control of the charge transfer toward TiO2 surface is provided for the first time. An increased amount of AcacH in the precursor promotes transition from preferential fast electron to preferential fast hole transfer toward anatase surface, correlating with a strong increase of the photocatalytic decomposition rate of organic pollutants. Suitable mechanisms of AcacH-induced passivation of electron traps at TiO2 surfaces are analyzed, providing a new degree of freedom for tailoring the properties of photocatalytic systems.