Mechanistic Insights of Ethanol Steam Reforming over Ni–CeO x (111): The Importance of Hydroxyl Groups for Suppressing Coke Formation

Liu, Zongyuan; Duchoň, Tomáš; Wang, Huanru; Peterson, Erik W.; Zhou, Yinghui; Luo, Si; Zhou, Jing; Matolín, Vladimir; Stacchiola, Dario J.; Rodriguez, José A.; Senanayake, Sanjaya D.

doi:10.1021/acs.jpcc.5b04310

Title: Mechanistic Insights of Ethanol Steam Reforming over Ni–CeO _x (111): The Importance of Hydroxyl Groups for Suppressing Coke Formation

Journal Article · Thu Jul 30 00:00:00 EDT 2015 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.5b04310· OSTI ID:1213370

Liu, Zongyuan ^[1]; Duchoň, Tomáš ^[2]; Wang, Huanru ^[3]; Peterson, Erik W. ^[4]; Zhou, Yinghui ^[4]; Luo, Si ^[1]; Zhou, Jing ^[4]; Matolín, Vladimir ^[2]; Stacchiola, Dario J. ^[5]; Rodriguez, José A. ^[1]; Senanayake, Sanjaya D. ^[5]

Stony Brook Univ., NY (United States). Dept. of Chemistry; Brookhaven National Lab. (BNL), Upton, NY (United States). Dept. of Chemistry
Charles Univ., Prague (Czech Republic). Faculty of Mathematics and Physics
Beijing Research Inst. of Chemical Industry (China). Analytical Research Division
Univ. of Wyoming, Laramie, WY (United States). Dept. of Chemistry
Brookhaven National Lab. (BNL), Upton, NY (United States). Dept. of Chemistry

We have studied the reaction of ethanol and water over Ni–CeO_2-x(111) model surfaces to elucidate the mechanistic steps associated with the ethanol steam reforming (ESR) reaction. Our results provide insights about the importance of hydroxyl groups to the ESR reaction over Ni-based catalysts. Systematically, we have investigated the reaction of ethanol on Ni–CeO_2-x(111) at varying Ce³⁺ concentrations (CeO_1.8–2.0) with absence/presence of water using a combination of soft X-ray photoelectron spectroscopy (sXPS) and temperature-programmed desorption (TPD). Consistent with previous reports, upon annealing, metallic Ni formed on reduced ceria while NiO was the main component on fully oxidized ceria. Ni⁰ is the active phase leading to both the C–C and C–H cleavage of ethanol but is also responsible for carbon accumulation or coking. We have identified a Ni₃C phase that formed prior to the formation of coke. At temperatures above 600K, the lattice oxygen from ceria and the hydroxyl groups from water interact cooperatively in the removal of coke, likely through a strong metal–support interaction between nickel and ceria that facilitates oxygen transfer.

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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:: 1213370

Report Number(s):: BNL-108216-2015-JA; R&D Project: CO009; KC0302010

Journal Information:: Journal of Physical Chemistry. C, Vol. 119, Issue 32; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 37 works

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Title: Mechanistic Insights of Ethanol Steam Reforming over Ni–CeO x (111): The Importance of Hydroxyl Groups for Suppressing Coke Formation

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Title: Mechanistic Insights of Ethanol Steam Reforming over Ni–CeO _x (111): The Importance of Hydroxyl Groups for Suppressing Coke Formation