Elucidation of Active Sites for the Reaction of Ethanol on TiO 2 /Au(111)

Boyle, David T.; Wilke, Jeremy A.; Palomino, Robert M.; Lam, Vivian H.; Schlosser, Daniel A.; Andahazy, Wil J.; Stopak, Cameron Z.; Stacchiola, Dario J.; Rodriguez, Jose A.; Baber, Ashleigh E.

doi:10.1021/acs.jpcc.6b11764

Title: Elucidation of Active Sites for the Reaction of Ethanol on TiO ₂ /Au(111)

Journal Article · Fri Mar 17 00:00:00 EDT 2017 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.6b11764· OSTI ID:1372450

Boyle, David T. ^[1]; Wilke, Jeremy A. ^[1]; Palomino, Robert M. ^[2]; Lam, Vivian H. ^[1]; Schlosser, Daniel A. ^[1]; Andahazy, Wil J. ^[1]; Stopak, Cameron Z. ^[1]; Stacchiola, Dario J. ^[3]; Rodriguez, Jose A. ^[2];

^[1]

James Madison Univ., Harrisonburg, VA (United States). Dept. of Chemistry and Biochemistry
Brookhaven National Lab. (BNL), Upton, NY (United States). Dept. of Chemistry
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials

Obtaining a molecular-level understanding of the reaction of alcohols with heterogeneous model catalysts is critical for improving industrial catalytic processes, such as the production of H₂ from alcohols. Gold has been shown to be an excellent oxidation catalyst once oxygen is added to it. The use of reducible oxides provides a source of oxygen on Au(111) for the reaction of ethanol, which is easily regenerated in the presence of an oxygen background. In this work, ethanol operates as a probe molecule to investigate the role of Au(111), TiO₂ nanoparticles, and TiO₂/Au interfacial surface sites on the catalytic properties of TiO₂/Au(111). Ultrahigh vacuum temperature-programmed desorption (TPD) studies with ethanol/Au(111) elucidate previously unreported adsorption sites for ethanol. Ethanol molecularly adsorbs to Au terrace sites, step edges, and undercoordinated kink sites with adsorption energies of -51.7, -55.8, and -65.1 kJ/mol, respectively. In a TPD coverage study of ethanol on TiO₂/Au(111) indicates ethanol undergoes dissociative adsorption to form H*(a) and CH₃CH₂O*(a) on the inverse model catalyst surface. The desorption temperature of low coverages of ethanol from TiO2/Au(111) (Tdes ≈ 235 K) is at an intermediate temperature between the desorption temperatures from bulk Au(111) and TiO₂(110), indicating both Au and TiO₂ play a role in the adsorption of ethanol. Both low-temperature adsorption and high-temperature reactions are studied and indicate that ethanol-derived products such as acetaldehyde and ethylene desorb from TiO₂/Au(111) at ~500 K. Here, we report the identification of catalytically active sites on TiO₂/Au(111) as interfacial sites between the oxide and Au(111) surface through the use of temperature-programmed desorption and infrared reflection absorption spectroscopy.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

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

Grant/Contract Number:: SC00112704

OSTI ID:: 1372450

Report Number(s):: BNL-114048-2017-JA; R&D Project: CO040; KC0302010

Journal Information:: Journal of Physical Chemistry. C, Vol. 121, Issue 14; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 17 works

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Title: Elucidation of Active Sites for the Reaction of Ethanol on TiO ₂ /Au(111)