Ultrafast Real-Time Dynamics of CO Oxidation over an Oxide Photocatalyst

ACS Catalysis 10,22, 13650 - 13658 (2020)

Ultrafast Real-Time Dynamics of CO Oxidation over an Oxide Photocatalyst

Michael Wagstaffe, Lukas Wenthaus, Adrian Dominguez-Castro, Simon Chung, Guilherme Dalla Lana Semione, Steffen Palutke, Giuseppe Mercurio, Siarhei Dziarzhytski, Harald Redlin, Nicolai Klemke, Yudong Yang, Thomas Frauenheim, Adriel Dominguez, Franz Kärtner, Angel Rubio, Wilfried Wurth, Andreas Stierle,, Heshmat Noei

Femtosecond X-ray laser pulses synchronized with an optical laser were employed to investigate the reaction dynamics of the photooxidation of CO on the anatase TiO2(101) surface in real time. Our time-resolved soft X-ray photoemission spectroscopy results provide evidence of ultrafast timescales and, coupled with theoretical calculations, clarify the mechanism of oxygen activation that is crucial to unraveling the underlying processes for a range of photocatalytic reactions relevant to air purification and self-cleaning surfaces. The reaction takes place between 1.2 and 2.8 (±0.2) ps after irradiation with an ultrashort laser pulse leading to the formation of CO2, prior to which no intermediate species were observed on a picosecond time scale. Our theoretical calculations predict that the presence of intragap unoccupied O2 levels leads to the formation of a charge-transfer complex. This allows the reaction to be initiated following laser illumination at a photon energy of 1.6 eV (770 nm), taking place via a proposed mechanism involving the direct transfer of electrons from TiO2 to physisorbed O2.

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http://dx.doi.org/https://doi.org/10.1021/acscatal.0c04098

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