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

Wagstaffe, M., Wenthaus, L., Dominguez-Castro, A., Chung, S., Lana Semione, G. D., Palutke, S., et al. (2020). Ultrafast Real-Time Dynamics of CO Oxidation over an Oxide Photocatalyst. ACS Catalysis, 10(22), 13650-13658. doi:10.1021/acscatal.0c04098.

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XP spectra of the C 1s and O 1s core levels showing the adsorption of CO and CO2 on anatase TiO2(101); XP spectra of the C 1s core level showing the adsorption and subsequent oxidation of CO to CO2 on anatase TiO2(101); XP spectra of the C 1s core level showing the effect of oxygen and X-ray exposure, in the absence of UV light, for CO on anatase TiO2(101); (a) time-resolved XP map of the Ti 2p3/2 core level as a function of delay time; time-resolved XP spectrum of the O 1s core level extracted on time zero in a 200 fs window; time-resolved XP spectra of the O 1s core level during the photooxidation of CO to CO2 on TiO2(101) displayed over a broader binding energy range; time-resolved XP spectra of the O 1s core level during the photooxidation of CO to CO2 on TiO2(101) integrated over a 1 ps window; time-averaged XP spectra showing the adsorption of water, at 533.5 eV, on the surface over a 2 h time period; DFT calculations describing the electronic and structural properties of the adsorption of CO and O2; theoretically calculated DOS for O2 adsorption, O2/CO coadsorption, and for the pristine TiO2 surface using DFTB approach and DOS for the O2 adsorbed system using the Perdew–Burke–Ernzerhof functional at the DFT level of theory; absorption spectra comparing the pristine TiO2 and the O2–TiO2 systems; time-averaged XP spectra of the O 1s core level showing the laser-induced desorption of CO; XP spectra of the Ti 2p, O 1s, and C 1s core levels spectra for the as-prepared anatase TiO2(101) surface; LEED pattern for the as-prepared anatase TiO2(101) surface; and XP spectra of the Ti 2p core level for the as-prepared anatase TiO2(101) surface and corresponding difference spectrum (PDF) | X-ray Photoemission spectra as a function of time showing the photoreaction in the O 1s core level (MP4)
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 Creators:
Wagstaffe, M.1, Author
Wenthaus, L.1, 2, Author
Dominguez-Castro, A.3, Author
Chung, S.1, 4, Author
Lana Semione, G. D.1, Author
Palutke, S.1, Author
Mercurio, G.5, Author
Dziarzhytski, S.1, Author
Redlin, H.1, Author
Klemke, N.2, Author
Yang, Y.2, Author
Frauenheim, T.3, 6, Author
Dominguez, A.3, 6, 7, 8, Author
Kärtner, F.2, Author
Rubio, A.2, 8, 9, 10, Author           
Wurth, W.1, 2, 4, Author
Stierle, A.1, 4, Author
Noei, H.1, Author
Affiliations:
1Deutsches Elektronen-Synchrotron, ou_persistent22              
2Center for Free-Electron Laser Science, ou_persistent22              
3Bremen Center for Computational Material Science (BCCMS), ou_persistent22              
4Fachbereich Physik Universität Hamburg, ou_persistent22              
5European XFEL GmbH, ou_persistent22              
6Computational Science and Applied Research Institute (CSAR), ou_persistent22              
7Beijing Computational Science Research Center (CSRC), ou_persistent22              
8Nano-Bio Spectroscopy Group, Departamento de Fisica de Materiales, Universidad del País Vasco, UPV/EHU, ou_persistent22              
9Theory Group, Theory Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society, ou_2266715              
10Center for Computational Quantum Physics, Flatiron Institute, ou_persistent22              

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 Abstract: 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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Language(s): eng - English
 Dates: 2020-10-282020-09-182020-11-102020-11-20
 Publication Status: Issued
 Pages: 9
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/acscatal.0c04098
 Degree: -

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Project name : -
Grant ID : 753874
Funding program : Horizon 2020 (H2020)
Funding organization : European Commission (EC)
Project name : This paper is dedicated to our dear colleague W.W., leading scientist of the FEL FLASH and lead scientist at DESY, who passed away unexpectedly on May 8, 2019. W.W. pioneered time-resolved photoemission at FLASH, which is the basis for the experimental part of this study. We appreciate his outstanding contribution to the field and miss the extremely valuable scientific discussions with him. M.W. acknowledges support from the Initiative and Networking Funds of the Helmholtz Association through ExNet-0002. This work is supported by the DFG within the excellence cluster Center for Ultrafast Imaging (CUI). A.D. and A.R. acknowledge financial support from the European Union’s Horizon 2020 research and innovation program under Marie Sklodowska-Curie grant agreement no. 753874 and from the European Research Council (ERC-2015-AdG-694097), Grupos Consolidados (IT1249-19), and SFB925. T.F. and A.D. acknowledge financial support from NSAF U1930402 and computational resources from the Beijing Computational Science Research Center. Further, the authors acknowledge the excellent support from the scientific and technical staff of FLASH and thank Dr. Martin Beye for useful discussions and comments.
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Title: ACS Catalysis
Source Genre: Journal
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Pages: - Volume / Issue: 10 (22) Sequence Number: - Start / End Page: 13650 - 13658 Identifier: ISSN: 2155-5435
ISSN: 2155-5435