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Title: Ambient pressure XPS and IRRAS investigation of ethanol steam reforming on Ni–CeO 2(111) catalysts: An in situ study of C–C and O–H bond scission

Ambient-Pressure X-ray Photoelectron Spectroscopy (AP-XPS) and Infrared Reflection Absorption Spectroscopy (AP-IRRAS) have been used to elucidate the active sites and mechanistic steps associated with the ethanol steam reforming reaction (ESR) over Ni–CeO 2(111) model catalysts. Our results reveal that surface layers of the ceria substrate are both highly reduced and hydroxylated under reaction conditions while the small supported Ni nanoparticles are present as Ni 0/NixC. A multifunctional, synergistic role is highlighted in which Ni, CeO x and the interface provide an ensemble effect in the active chemistry that leads to H 2. Ni 0 is the active phase leading to both C–C and C–H bond cleavage in ethanol and it is also responsible for carbon accumulation. On the other hand, CeO x is important for the deprotonation of ethanol/water to ethoxy and OH intermediates. The active state of CeO x is a Ce 3+(OH) x compound that results from extensive reduction by ethanol and the efficient dissociation of water. Additionally, we gain an important insight into the stability and selectivity of the catalyst by its effective water dissociation, where the accumulation of surface carbon can be mitigated by the increased presence of surface OH groups. As a result, the co-existencemore » and cooperative interplay of Ni 0 and Ce 3+(OH) x through a metal–support interaction facilitate oxygen transfer, activation of ethanol/water as well as the removal of coke.« less
Authors:
 [1] ;  [2] ;  [3] ;  [3] ;  [3] ;  [4] ;  [5] ;  [5] ;  [5] ;  [2] ;  [3] ;  [1] ;  [3]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ.,Stony Brook, NY (United States)
  2. Charles Univ. in Prague (Czech Republic)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
  4. Univ. of Wyoming, Laramie, WY (United States)
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Report Number(s):
BNL-113212-2016-JA
Journal ID: ISSN 1463-9076; PPCPFQ; R&D Project: CO040; KC0302010
Grant/Contract Number:
SC0012704; AC02-05CH11231
Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 18; Journal Issue: 25; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1333206
Alternate Identifier(s):
OSTI ID: 1378777

Liu, Zongyuan, Duchon, Tomas, Wang, Huanru, Grinter, David C., Waluyo, Iradwikanari, Zhou, Jing, Liu, Qiang, Jeong, Beomgyun, Crumlin, Ethan J., Matolin, Vladimir, Stacchiola, Dario J., Rodriguez, Jose A., and Senanayake, Sanjaya D.. Ambient pressure XPS and IRRAS investigation of ethanol steam reforming on Ni–CeO2(111) catalysts: An in situ study of C–C and O–H bond scission. United States: N. p., Web. doi:10.1039/c6cp01212d.
Liu, Zongyuan, Duchon, Tomas, Wang, Huanru, Grinter, David C., Waluyo, Iradwikanari, Zhou, Jing, Liu, Qiang, Jeong, Beomgyun, Crumlin, Ethan J., Matolin, Vladimir, Stacchiola, Dario J., Rodriguez, Jose A., & Senanayake, Sanjaya D.. Ambient pressure XPS and IRRAS investigation of ethanol steam reforming on Ni–CeO2(111) catalysts: An in situ study of C–C and O–H bond scission. United States. doi:10.1039/c6cp01212d.
Liu, Zongyuan, Duchon, Tomas, Wang, Huanru, Grinter, David C., Waluyo, Iradwikanari, Zhou, Jing, Liu, Qiang, Jeong, Beomgyun, Crumlin, Ethan J., Matolin, Vladimir, Stacchiola, Dario J., Rodriguez, Jose A., and Senanayake, Sanjaya D.. 2016. "Ambient pressure XPS and IRRAS investigation of ethanol steam reforming on Ni–CeO2(111) catalysts: An in situ study of C–C and O–H bond scission". United States. doi:10.1039/c6cp01212d. https://www.osti.gov/servlets/purl/1333206.
@article{osti_1333206,
title = {Ambient pressure XPS and IRRAS investigation of ethanol steam reforming on Ni–CeO2(111) catalysts: An in situ study of C–C and O–H bond scission},
author = {Liu, Zongyuan and Duchon, Tomas and Wang, Huanru and Grinter, David C. and Waluyo, Iradwikanari and Zhou, Jing and Liu, Qiang and Jeong, Beomgyun and Crumlin, Ethan J. and Matolin, Vladimir and Stacchiola, Dario J. and Rodriguez, Jose A. and Senanayake, Sanjaya D.},
abstractNote = {Ambient-Pressure X-ray Photoelectron Spectroscopy (AP-XPS) and Infrared Reflection Absorption Spectroscopy (AP-IRRAS) have been used to elucidate the active sites and mechanistic steps associated with the ethanol steam reforming reaction (ESR) over Ni–CeO2(111) model catalysts. Our results reveal that surface layers of the ceria substrate are both highly reduced and hydroxylated under reaction conditions while the small supported Ni nanoparticles are present as Ni0/NixC. A multifunctional, synergistic role is highlighted in which Ni, CeOx and the interface provide an ensemble effect in the active chemistry that leads to H2. Ni0 is the active phase leading to both C–C and C–H bond cleavage in ethanol and it is also responsible for carbon accumulation. On the other hand, CeOx is important for the deprotonation of ethanol/water to ethoxy and OH intermediates. The active state of CeOx is a Ce3+(OH)x compound that results from extensive reduction by ethanol and the efficient dissociation of water. Additionally, we gain an important insight into the stability and selectivity of the catalyst by its effective water dissociation, where the accumulation of surface carbon can be mitigated by the increased presence of surface OH groups. As a result, the co-existence and cooperative interplay of Ni0 and Ce3+(OH)x through a metal–support interaction facilitate oxygen transfer, activation of ethanol/water as well as the removal of coke.},
doi = {10.1039/c6cp01212d},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 25,
volume = 18,
place = {United States},
year = {2016},
month = {3}
}

Works referenced in this record:

Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering
journal, September 2006
  • Huber, George W.; Iborra, Sara; Corma, Avelino
  • Chemical Reviews, Vol. 106, Issue 9, p. 4044-4098
  • DOI: 10.1021/cr068360d