Dynamics of CO photooxidation to CO2 on rutile (110)

Free-electron lasers (FELs) enable the study of the ultrafast dynamics of photocatalytic reactions by time-resolved X-ray photoelectron spectroscopy (tr-XPS) with femtosecond time resolution. In an optical pump - soft X-ray probe photoemission experiment conducted at the free-electron laser in Hamburg (FLASH), we observed the ultrafast oxidation of CO to CO2 on rutile TiO2(110) by monitoring the O 1s core level region. Within 800± 250 fs after laser excitation, CO2 as a product of the photooxidation of CO is detected. Based on density functional theory calculations, we propose that the oxygen activation pathway for the CO oxidation is initiated via an O2-TiO2 charge transfer complex directly excited by the 770 nm pump laser. Our results give insight into the fundemental understanding of photocatalytic processes of TiO2 polymorphs relevant for the design of more efficient photoctalaysts.