Room-temperature activation of methane and dry re-forming with CO2 on Ni-CeO2 (111) surfaces: Effect of Ce3+ sites and metal–support interactions on C–H bond cleavage

Lustemberg, Pablo G.; Ramírez, Pedro J.; Liu, Zongyuan; Gutierrez, Ramon A.; Grinter, David G.; Carrasco, Javier; Senanayake, Sanjaya D.; Rodriguez, Jose A.; Ganduglia-Pirovano, M. Veronica

doi:10.1021/acscatal.6b02360

Room-temperature activation of methane and dry re-forming with CO₂ on Ni-CeO₂ (111) surfaces: Effect of Ce³⁺ sites and metal–support interactions on C–H bond cleavage

Journal Article · Thu Oct 27 00:00:00 EDT 2016 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.6b02360· OSTI ID:1333201

Lustemberg, Pablo G. ^[1]; Ramírez, Pedro J. ^[2]; Liu, Zongyuan ^[3]; Gutierrez, Ramon A. ^[2]; Grinter, David G. ^[3]; Carrasco, Javier ^[4]; Senanayake, Sanjaya D. ^[5]; Rodriguez, Jose A. ^[6]; Ganduglia-Pirovano, M. Veronica ^[7]

Instituto de Fisica Rosario (IFIR, CONICET-UNR), Santa Fe (Argentina)
Univ. Central de Venezuela, Caracas (Venezuela)
State Univ. of New York, Stony Brook, NY (United States)
CIC Energigune, Alava (Spain)
Brookhaven National Lab. (BNL), Upton, NY (United States)
State Univ. of New York, Stony Brook, NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
Instituto de Catalisis y Petroleoquimica (ICP-CSIC), Madrid (Spain)

The results of core-level photoemission indicate that Ni-CeO₂(111) surfaces with small or medium coverages of nickel are able to activate methane at 300 K, producing adsorbed CH_x and CO_x (x = 2, 3) groups. Calculations based on density functional theory predict a relatively low activation energy of 0.6–0.7 eV for the cleavage of the first C–H bond in the adsorbed methane molecule. Ni and O centers of ceria work in a cooperative way in the dissociation of the C–H bond at room temperature, where a low Ni loading is crucial for the catalyst activity and stability. The strong electronic perturbations in the Ni nanoparticles produced by the ceria supports of varying natures, such as stoichiometric and reduced, result in a drastic change in their chemical properties toward methane adsorption and dissociation as well as the dry reforming of methane reaction. Lastly, the coverage of Ni has a drastic effect on the ability of the system to dissociate methane and catalyze the dry re-forming process.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

OSTI ID:: 1333201

Report Number(s):: BNL--113197-2016-JA; KC0302010

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis; ISSN 2155-5435

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Dry reforming of methane on a highly-active Ni-CeO₂ catalyst: Effects of metal-support interactions on C–H bond breaking

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
DFT
XPS
ceria
dry re-forming
methane activation
nickel
support effect
supported catalysts