Title: Adsorption and activation of CO₂ on Pt/CeOx/TiO₂(110): Role of the Pt-CeO_x interface

Abstract

The adsorption and dissociation of CO₂ on TiO₂(110), CeO_x/TiO₂(110) and Pt/CeO_x/TiO₂(110) surfaces has been examined using Ambient Pressure X-ray Photoelectron Spectroscopy (AP-XPS). The substrates under study exhibited different degrees of complexity which were tested for the binding of the adsorbate and the cleavage of C-O bonds. The surfaces were prepared by depositing CeO_x (0.1 ML) onto TiO₂(110) to form a mixed oxide support, onto which Pt nanoparticles (0.2 ML) were deposited. This configuration yields a complex set of interfaces between metal and oxides and we have systematically titrated the active role of each component (Pt 4f, Ce 3d and Ti 2p regions) and the arising surface intermediates (C 1s and O 1s regions). CO₂ barely bonds to stoichiometric TiO₂(110). It heals oxygen vacancies of this oxide surface (CO_2,gas → CO_gas + O_a) and does not form stable carbonates. A stable carbonate was seen upon adsorption of CO₂ on CeO_x/TiO₂(110) and on this type of substrate the adsorbate also removed O vacancies leading to the oxidation of Ti³⁺and Ce³⁺ sites. Pt nanoparticles dispersed on CeO_x/TiO₂(110) were highly effective for the binding and dissociation of CO₂, with the formation of CO₃, CO, C and CH_x species on the Pt/CeO_x/TiO₂(110) system. The resultsmore » of theoretical calculations based on density-functional theory (DFT) show that Pt/CeOx/TiO2(110) binds CO2 much stronger than surfaces of bulk platinum {(111), (100), (110)} or other late transition metals. On a Pt-CeO_x interface, the molecule adsorbs with a bent configuration (~ 130° O-C-O bond angle) and with a substantial elongation (~ 0.1 Å) of the C-O bonds, facilitating its transformation into high value chemicals.« less

Authors:

Grinter, David C. ^[1]; Graciani, Jesús  ^[2];

• Search DOE PAGES for author "Graciani, Jesús"
• Search DOE PAGES for ORCID "0000-0003-4791-0127"

Palomino, Robert M.  ^[3];

• Search DOE PAGES for author "Palomino, Robert M."
• Search DOE PAGES for ORCID "0000-0003-4476-3512"

Xu, Fang ^[4]; Waluyo, Iradwikanari ^[5]; Sanz, Javier Fdez ^[2]; Senanayake, Sanjaya D. ^[3]; Rodriguez, José A.  ^[4]

• Search DOE PAGES for author "Rodriguez, José A."
• Search DOE PAGES for ORCID "0000-0002-5680-4214"

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+ Show Author Affiliations

1. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Div.; Science and Technology Facilities Council (STFC), Oxford (United Kingdom). Diamond Light Source, Ltd.
2. Univ. of Sevilla (Spain). Dept. de Quimica Fisica
3. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Div.
4. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Div.; Univ. of Texas at San Antonio, TX (United States). Dept. of Chemistry
5. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

Publication Date:

Tue Apr 20 00:00:00 EDT 2021

Research Org.:

Brookhaven National Lab. (BNL), Upton, NY (United States)

Sponsoring Org.:

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

OSTI Identifier:

1778799

Alternate Identifier(s):

OSTI ID: 1779323

Report Number(s):

BNL-221312-2021-JAAM
Journal ID: ISSN 0039-6028

Grant/Contract Number:  

SC0012704

Resource Type:

Accepted Manuscript

Journal Name:

Surface Science

Additional Journal Information:

Journal Volume: 710; Journal ID: ISSN 0039-6028

Publisher:

Elsevier

Country of Publication:

United States

Language:

English

Subject:

36 MATERIALS SCIENCE; Carbon dioxide; platinum; ceria; titania; ambient-pressure x-ray photoelectron spectroscopy; density functional calculations