Methanol on Anatase TiO 2 (101): Mechanistic Insights into Photocatalysis

Setvin, Martin; Shi, Xiao; Hulva, Jan; Simschitz, Thomas; Parkinson, Gareth S.; Schmid, Michael; Di Valentin, Cristiana; Selloni, Annabella; Diebold, Ulrike

doi:10.1021/acscatal.7b02003

Title: Methanol on Anatase TiO ₂ (101): Mechanistic Insights into Photocatalysis

Journal Article · Thu Sep 21 00:00:00 EDT 2017 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.7b02003· OSTI ID:1393722

^[1]; Shi, Xiao ^[2]; Hulva, Jan ^[1]; Simschitz, Thomas ^[1]; Parkinson, Gareth S. ^[1]; Schmid, Michael ^[1];

^[3];

^[2]; Diebold, Ulrike ^[1]

Institute of Applied Physics, TU Wien, Wiedner Hauptstrasse 8-10/134, 1040 Vienna, Austria
Department of Chemistry, Princeton University, Frick Laboratory, Princeton, New Jersey 08544, United States
Dipartimento di Scienza dei Materiali, Università di Milano-Bicocca, Via Cozzi 55, 20125 Milano, Italy

The photoactivity of methanol adsorbed on the anatase TiO₂ (101) surface was studied by a combination of scanning tunneling microscopy (STM), temperature-programmed desorption (TPD), X-ray photoemission spectroscopy (XPS), and density functional theory (DFT) calculations. Isolated methanol molecules adsorbed at the anatase (101) surface show a negligible photoactivity. Two ways of methanol activation were found. First, methoxy groups formed by reaction of methanol with coadsorbed O₂ molecules or terminal OH groups are photoactive, and they turn into formaldehyde upon UV illumination. The methoxy species show an unusual C 1s core-level shift of 1.4 eV compared to methanol; their chemical assignment was verified by DFT calculations with inclusion of final-state effects. The second way of methanol activation opens at methanol coverages above 0.5 monolayer (ML), and methyl formate is produced in this reaction pathway. The adsorption of methanol in the coverage regime from 0 to 2 ML is described in detail; it is key for understanding the photocatalytic behavior at high coverages. There, a hydrogen-bonding network is established in the adsorbed methanol layer, and consequently, methanol dissociation becomes energetically more favorable. DFT calculations show that dissociation of the methanol molecule is always the key requirement for hole transfer from the substrate to the adsorbed methanol. Here, we show that the hydrogen-bonding network established in the methanol layer dramatically changes the kinetics of proton transfer during the photoreaction.

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Research Organization:: Princeton Univ., NJ (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0007347

OSTI ID:: 1393722

Alternate ID(s):: OSTI ID: 1499011

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Vol. 7 Journal Issue: 10; ISSN 2155-5435

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 73 works

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33 ADVANCED PROPULSION SYSTEMS
anatase
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photocatalysis
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Title: Methanol on Anatase TiO 2 (101): Mechanistic Insights into Photocatalysis

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Title: Methanol on Anatase TiO ₂ (101): Mechanistic Insights into Photocatalysis