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

Abstract

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.

Authors:

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

Publication Date:: Thu Jul 30 00:00:00 EDT 2015

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

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

OSTI Identifier:: 1213370

Report Number(s):: BNL-108216-2015-JA
Journal ID: ISSN 1932-7447; R&D Project: CO009; KC0302010

Grant/Contract Number:: SC00112704

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. C

Additional Journal Information:: Journal Volume: 119; Journal Issue: 32; Journal ID: ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; ethanol; reforming; H₂ production; ceria; nickel; X-ray photoelectron spectroscopy; temperature programmed desorption

Citation Formats


                    Liu, Zongyuan, Duchoň, Tomáš, Wang, Huanru, Peterson, Erik W., Zhou, Yinghui, Luo, Si, Zhou, Jing, Matolín, Vladimir, Stacchiola, Dario J., Rodriguez, José A., and Senanayake, Sanjaya D. Mechanistic Insights of Ethanol Steam Reforming over Ni–CeO x (111): The Importance of Hydroxyl Groups for Suppressing Coke Formation.  United States: N. p., 2015. 
Web.  doi:10.1021/acs.jpcc.5b04310.

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                    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. Mechanistic Insights of Ethanol Steam Reforming over Ni–CeO x (111): The Importance of Hydroxyl Groups for Suppressing Coke Formation.  United States.  https://doi.org/10.1021/acs.jpcc.5b04310

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                    Liu, Zongyuan, Duchoň, Tomáš, Wang, Huanru, Peterson, Erik W., Zhou, Yinghui, Luo, Si, Zhou, Jing, Matolín, Vladimir, Stacchiola, Dario J., Rodriguez, José A., and Senanayake, Sanjaya D. Thu .  
"Mechanistic Insights of Ethanol Steam Reforming over Ni–CeO x (111): The Importance of Hydroxyl Groups for Suppressing Coke Formation".  United States.  https://doi.org/10.1021/acs.jpcc.5b04310.  https://www.osti.gov/servlets/purl/1213370.

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@article{osti_1213370,

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

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

  abstractNote = {We have studied the reaction of ethanol and water over Ni–CeO2-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–CeO2-x(111) at varying Ce³⁺ concentrations (CeO1.8–2.0) 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.},

  doi          = {10.1021/acs.jpcc.5b04310},

  journal      = {Journal of Physical Chemistry. C},

  number       = 32,

  volume       = 119,

  place        = {United States},

  year         = {Thu Jul 30 00:00:00 EDT 2015},

  month        = {Thu Jul 30 00:00:00 EDT 2015}

}

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Works referenced in this record:

Electronic Metal–Support Interactions and the Production of Hydrogen Through the Water-Gas Shift Reaction and Ethanol Steam Reforming: Fundamental Studies with Well-Defined Model Catalysts
journal, August 2013

Senanayake, Sanjaya D.; Rodriguez, José A.; Stacchiola, Dario
Topics in Catalysis, Vol. 56, Issue 15-17
DOI: 10.1007/s11244-013-0148-5

Interaction of Methanol with Well-Defined Ceria Surfaces: Reflection/Absorption Infrared Spectroscopy, X-ray Photoelectron Spectroscopy, and Temperature-Programmed Desorption Study
journal, August 1999

Siokou, A.; Nix, R. M.
The Journal of Physical Chemistry B, Vol. 103, Issue 33
DOI: 10.1021/jp991127h

Steam Reforming of Ethanol on Ni/CeO ₂ : Reaction Pathway and Interaction between Ni and the CeO ₂ Support
journal, April 2013

Xu, Wenqian; Liu, Zongyuan; Johnston-Peck, Aaron C.
ACS Catalysis, Vol. 3, Issue 5
DOI: 10.1021/cs4000969

Adsorption and reaction of formaldehyde on thin-film cerium oxide
journal, April 2006

Zhou, J.; Mullins, D. R.
Surface Science, Vol. 600, Issue 7
DOI: 10.1016/j.susc.2006.02.009

Tailoring the Properties of Atomic Layer Deposited Nickel and Nickel Carbide Thin Films via Chain-Length Control of the Alcohol Reducing Agents
journal, September 2014

Sarr, Mouhamadou; Bahlawane, Naoufal; Arl, Didier
The Journal of Physical Chemistry C, Vol. 118, Issue 40
DOI: 10.1021/jp5068318

The Unique Properties of the Oxide-Metal Interface: Reaction of Ethanol on an Inverse Model CeO _x –Au(111) Catalyst
journal, October 2014

Senanayake, S. D.; Mudiyanselage, K.; Bruix, A.
The Journal of Physical Chemistry C, Vol. 118, Issue 43
DOI: 10.1021/jp507966v

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

Bond activation sequence observed in the chemisorption and surface reaction of ethanol on Ni(111)
journal, May 1986

Gates, S. M.; Russell, J. N.; Yates, J. T.
Surface Science, Vol. 171, Issue 1
DOI: 10.1016/0039-6028(86)90565-0

Characterization of surface processes at the Ni-based catalyst during the methanation of biomass-derived synthesis gas: X-ray photoelectron spectroscopy (XPS)
journal, October 2007

Czekaj, Izabela; Loviat, Francois; Raimondi, Fabio
Applied Catalysis A: General, Vol. 329
DOI: 10.1016/j.apcata.2007.06.027

The structure of CO on Ni(111)
journal, January 1982

Netzer, Falko P.; Madey, Theodore E.
The Journal of Chemical Physics, Vol. 76, Issue 1
DOI: 10.1063/1.442674

H2 production for MC fuel cell by steam reforming of ethanol over MgO supported Pd, Rh, Ni and Co catalysts
journal, October 2004

Frusteri, F.; Freni, S.; Spadaro, L.
Catalysis Communications, Vol. 5, Issue 10
DOI: 10.1016/j.catcom.2004.07.015

Ethanol steam reforming over Co-based catalysts: Role of oxygen mobility
journal, January 2009

Song, H.; Ozkan, U.
Journal of Catalysis, Vol. 261, Issue 1
DOI: 10.1016/j.jcat.2008.11.006

Thermal Chemistry of Iodomethane on Ni(110). 1. Clean and Hydrogen-Predosed Surfaces
journal, October 2004

Guo, Hansheng; Zaera, Francisco
The Journal of Physical Chemistry B, Vol. 108, Issue 41
DOI: 10.1021/jp047009y

Methyl iodide thermal reactions when chemisorbed on nickel(100) surfaces
journal, September 1992

Tjandra, Sariwan; Zaera, Francisco
Langmuir, Vol. 8, Issue 9
DOI: 10.1021/la00045a004

Water Dissociation on CeO ₂ (100) and CeO ₂ (111) Thin Films
journal, August 2012

Mullins, David R.; Albrecht, Peter M.; Chen, Tsung-Liang
The Journal of Physical Chemistry C, Vol. 116, Issue 36
DOI: 10.1021/jp306444h

Reforming of Oxygenates for H ₂ Production: Correlating Reactivity of Ethylene Glycol and Ethanol on Pt(111) and Ni/Pt(111) with Surface d-Band Center
journal, February 2006

Skoplyak, Orest; Barteau, Mark A.; Chen, Jingguang G.
The Journal of Physical Chemistry B, Vol. 110, Issue 4
DOI: 10.1021/jp0548927

IRAS study of the adsorption of CO on Ni(111): Interrelation between various bonding modes of chemisorbed CO
journal, January 1988

Surnev, L.; Xu, Z.; Yates, J. T.
Surface Science, Vol. 201, Issue 1-2
DOI: 10.1016/0039-6028(88)90593-6

Reduction Characteristics of Ceria under Ethanol Steam Reforming Conditions: Effect of the Particle Size
journal, December 2013

Soykal, I. Ilgaz; Sohn, Hyuntae; Singh, Deepika
ACS Catalysis, Vol. 4, Issue 2
DOI: 10.1021/cs400908h

Adsorption and Reaction of C ₁ −C ₃ Alcohols over CeO _X (111) Thin Films
journal, July 2010

Mullins, D. R.; Senanayake, S. D.; Chen, T. -L.
The Journal of Physical Chemistry C, Vol. 114, Issue 40
DOI: 10.1021/jp103905e

Use of biofuels to produce hydrogen (reformation processes)
journal, January 2008

Piscina, Pilar Ramírez de la; Homs, Narcís
Chemical Society Reviews, Vol. 37, Issue 11
DOI: 10.1039/b712181b

Nickel Mg K _α XPS Spectra from the Physical Electronics Model 5400 Spectrometer
journal, July 1994

Mansour, A. N.
Surface Science Spectra, Vol. 3, Issue 3
DOI: 10.1116/1.1247749

Water–Gas Shift and CO Methanation Reactions over Ni–CeO2(111) Catalysts
journal, January 2011

Senanayake, Sanjaya D.; Evans, Jaime; Agnoli, Stefano
Topics in Catalysis, Vol. 54, Issue 1-4
DOI: 10.1007/s11244-011-9645-6

The catalytic synthesis of hydrocarbons from H2/CO mixtures over the group VIII metals IV. The kinetic behavior of CO hydrogenation over Ni catalysts
journal, July 1976

Vannice, M.
Journal of Catalysis, Vol. 44, Issue 1
DOI: 10.1016/0021-9517(76)90384-5

Reaction network of steam reforming of ethanol over Ni-based catalysts
journal, July 2004

Fatsikostas, A.
Journal of Catalysis, Vol. 225, Issue 2
DOI: 10.1016/j.jcat.2004.04.034

Influence of Hydroxyls on Pd Atom Mobility and Clustering on Rutile TiO ₂ (011)-2 × 1
journal, May 2014

Addou, Rafik; Senftle, Thomas P.; O’Connor, Nolan
ACS Nano, Vol. 8, Issue 6
DOI: 10.1021/nn501817w

Support effects in cobalt-based ethanol steam reforming catalysts: Reaction of ethanol on Co/CeO2/YSZ(100) model catalysts
journal, July 2012

Martono, Eddie; Vohs, John M.
Journal of Catalysis, Vol. 291
DOI: 10.1016/j.jcat.2012.04.010

Interplay between particle size, composition, and structure of MgAl2O4-supported Co–Cu catalysts and their influence on carbon accumulation during steam reforming of ethanol
journal, November 2013

Ávila-Neto, C. N.; Zanchet, D.; Hori, C. E.
Journal of Catalysis, Vol. 307
DOI: 10.1016/j.jcat.2013.07.025

Efficient Production of Hydrogen over Supported Cobalt Catalysts from Ethanol Steam Reforming
journal, July 2002

Llorca, Jordi; Homs, Narcı́s; Sales, Joaquim
Journal of Catalysis, Vol. 209, Issue 2
DOI: 10.1006/jcat.2002.3643

Interactions of alcohols with a nickel oxide(100) surface studied by high-resolution electron energy loss spectroscopy and temperature-programmed desorption spectroscopy
journal, September 1993

Wu, Ming Cheng; Truong, Charles M.; Goodman, D. Wayne
The Journal of Physical Chemistry, Vol. 97, Issue 37
DOI: 10.1021/j100139a029

Ethanol steam reforming over Ni and Ni–Cu catalysts
journal, August 2009

Wang, Fagen; Li, Yong; Cai, Weijie
Catalysis Today, Vol. 146, Issue 1-2
DOI: 10.1016/j.cattod.2009.01.027

The ethanol steam reforming over Cu-Ni/SiO2 catalysts: Effect of Cu/Ni ratio
journal, August 2011

Chen, Li-Chung; Lin, Shawn D.
Applied Catalysis B: Environmental, Vol. 106, Issue 3-4
DOI: 10.1016/j.apcatb.2011.06.028

Interactions of Ni Nanoparticles with Reducible CeO ₂ (111) Thin Films
journal, April 2012

Zhou, Yinghui; Zhou, Jing
The Journal of Physical Chemistry C, Vol. 116, Issue 17
DOI: 10.1021/jp300259y

High Activity of Ce1−xNixO2−y for H2 Production through Ethanol Steam Reforming: Tuning Catalytic Performance through Metal-Oxide Interactions
journal, November 2010

Zhou, Gong; Barrio, Laura; Agnoli, Stefano
Angewandte Chemie, Vol. 122, Issue 50
DOI: 10.1002/ange.201004966

X-ray photoelectron spectroscopic study of magnetron sputtered carbon–nickel composite films
journal, September 2008

Kovács, Gy. J.; Bertóti, I.; Radnóczi, G.
Thin Solid Films, Vol. 516, Issue 21
DOI: 10.1016/j.tsf.2008.06.005

Production of Hydrogen from Ethanol: Review of Reaction Mechanism and Catalyst Deactivation
journal, April 2012

Mattos, Lisiane V.; Jacobs, Gary; Davis, Burtron H.
Chemical Reviews, Vol. 112, Issue 7
DOI: 10.1021/cr2000114

Hollow Fibers Networked with Perovskite Nanoparticles for H2 Production from Heavy Oil
journal, October 2013

Jeon, Yukwon; Park, Dae-Hwan; Park, Joo-Il
Scientific Reports, Vol. 3, Issue 1
DOI: 10.1038/srep02902

Mechanism of Ethanol Reforming: Theoretical Foundations
journal, March 2009

Wang, Jeng-Han; Lee, C. S.; Lin, M. C.
The Journal of Physical Chemistry C, Vol. 113, Issue 16
DOI: 10.1021/jp810307h

Adsorption and reaction of methanol on thin-film cerium oxide
journal, April 2006

Mullins, D. R.; Robbins, M. D.; Zhou, J.
Surface Science, Vol. 600, Issue 7
DOI: 10.1016/j.susc.2006.02.011

A Study of the Thermal Reactions of Methyl Iodide Coadsorbed with Hydrogen on Ni(111) Surfaces: Hydrogenation of Methyl Species to Methane
journal, June 1994

Tjandra, S.; Zaera, F.
Journal of Catalysis, Vol. 147, Issue 2
DOI: 10.1006/jcat.1994.1176

Theoretical Studies of the Adsorption of CO and C on Ni(111) and Ni/CeO ₂ (111): Evidence of a Strong Metal–Support Interaction
journal, April 2013

Carrasco, Javier; Barrio, Laura; Liu, Ping
The Journal of Physical Chemistry C, Vol. 117, Issue 16
DOI: 10.1021/jp400430r

High-pressure catalytic reactions over single-crystal metal surfaces
journal, November 1991

Rodriguez, JoséA.; Wayne Goodman, D.
Surface Science Reports, Vol. 14, Issue 1-2
DOI: 10.1016/0167-5729(91)90002-F

Electron spectroscopy of single crystal and polycrystalline cerium oxide surfaces
journal, July 1998

Mullins, D. R.; Overbury, S. H.; Huntley, D. R.
Surface Science, Vol. 409, Issue 2
DOI: 10.1016/S0039-6028(98)00257-X

In-situ FT-IRAS study of the CO oxidation reaction over Ru(001)
journal, August 1991

Hoffmann, F. M.; Weisel, M. D.; Peden, C. H. F.
Surface Science, Vol. 253, Issue 1-3
DOI: 10.1016/0039-6028(91)90581-C

Surface Defect Characterization in Oxygen-Dosed Nickel Surfaces and in NiO Thin Films by CO Adsorption−Desorption Experiments
journal, October 1997

Öfner, Helmut; Zaera, Francisco
The Journal of Physical Chemistry B, Vol. 101, Issue 44
DOI: 10.1021/jp971854h

Superior performance of Ni–W–Ce mixed-metal oxide catalysts for ethanol steam reforming: Synergistic effects of W- and Ni-dopants
journal, January 2015

Liu, Zongyuan; Xu, Wenqian; Yao, Siyu
Journal of Catalysis, Vol. 321
DOI: 10.1016/j.jcat.2014.10.017

Formation of metastable phases of Ni-C
journal, September 1992

Tanaka, T.; Ishihara, K. N.; Shingu, P. H.
Metallurgical Transactions A, Vol. 23, Issue 9
DOI: 10.1007/BF02658046

The Electronic Structure and Chemical Properties of a Ni/CeO ₂ Anode in a Solid Oxide Fuel Cell: A DFT + U Study
journal, November 2010

Shishkin, M.; Ziegler, T.
The Journal of Physical Chemistry C, Vol. 114, Issue 49
DOI: 10.1021/jp105316p

Correlation of Oxygen Storage Capacity and Structural Distortion in Transition-Metal-, Noble-Metal-, and Rare-Earth-Ion-Substituted CeO ₂ from First Principles Calculation
journal, September 2010

Gupta, Asha; Waghmare, U. V.; Hegde, M. S.
Chemistry of Materials, Vol. 22, Issue 18
DOI: 10.1021/cm101145d

Effect of Ceria Support on the Structure of Ni Nanoparticles
journal, April 2010

Zhou, Yinghui; Perket, Justin M.; Crooks, Adam B.
The Journal of Physical Chemistry Letters, Vol. 1, Issue 9
DOI: 10.1021/jz1003044

An STM study of carbon-induced structures on Ni(111): evidence for a carbidic-phase clock reconstruction
journal, November 1995

Klink, C.; Stensgaard, I.; Besenbacher, F.
Surface Science, Vol. 342, Issue 1-3
DOI: 10.1016/0039-6028(95)00697-4

The role of the catalytic particle in the growth of carbon nanotubes by plasma enhanced chemical vapor deposition
journal, June 2004

Ducati, C.; Alexandrou, I.; Chhowalla, M.
Journal of Applied Physics, Vol. 95, Issue 11
DOI: 10.1063/1.1728293

The influence of nano-architectured CeO supports in RhPd/CeO2 for the catalytic ethanol steam reforming reaction
journal, September 2015

Divins, N. J.; Casanovas, A.; Xu, W.
Catalysis Today, Vol. 253
DOI: 10.1016/j.cattod.2014.12.042

Ordered cerium oxide thin films grown on Ru(0001) and Ni(111)
journal, June 1999

Mullins, D.R.; Radulovic, P.V.; Overbury, S.H.
Surface Science, Vol. 429, Issue 1-3, p. 186-198
DOI: 10.1016/S0039-6028(99)00369-6

In Situ and Theoretical Studies for the Dissociation of Water on an Active Ni/CeO ₂ Catalyst: Importance of Strong Metal-Support Interactions for the Cleavage of O-H Bonds
journal, February 2015

Carrasco, Javier; López-Durán, David; Liu, Zongyuan
Angewandte Chemie International Edition, Vol. 54, Issue 13
DOI: 10.1002/anie.201410697

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journal, January 2019

Matus, Ekaterina V.; Okhlopkova, Lyudmila B.; Sukhova, Olga B.
Journal of Nanoparticle Research, Vol. 21, Issue 1
DOI: 10.1007/s11051-018-4454-5

Ceria-based model catalysts: fundamental studies on the importance of the metal–ceria interface in CO oxidation, the water–gas shift, CO ₂ hydrogenation, and methane and alcohol reforming
journal, January 2017

Rodriguez, José A.; Grinter, David C.; Liu, Zongyuan
Chemical Society Reviews, Vol. 46, Issue 7
DOI: 10.1039/c6cs00863a

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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

Abstract

Citation Formats

Electronic Metal–Support Interactions and the Production of Hydrogen Through the Water-Gas Shift Reaction and Ethanol Steam Reforming: Fundamental Studies with Well-Defined Model Catalysts journal, August 2013

Interaction of Methanol with Well-Defined Ceria Surfaces: Reflection/Absorption Infrared Spectroscopy, X-ray Photoelectron Spectroscopy, and Temperature-Programmed Desorption Study journal, August 1999

Steam Reforming of Ethanol on Ni/CeO 2 : Reaction Pathway and Interaction between Ni and the CeO 2 Support journal, April 2013

Adsorption and reaction of formaldehyde on thin-film cerium oxide journal, April 2006

Tailoring the Properties of Atomic Layer Deposited Nickel and Nickel Carbide Thin Films via Chain-Length Control of the Alcohol Reducing Agents journal, September 2014

The Unique Properties of the Oxide-Metal Interface: Reaction of Ethanol on an Inverse Model CeO x –Au(111) Catalyst journal, October 2014

Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering journal, September 2006

Bond activation sequence observed in the chemisorption and surface reaction of ethanol on Ni(111) journal, May 1986

Characterization of surface processes at the Ni-based catalyst during the methanation of biomass-derived synthesis gas: X-ray photoelectron spectroscopy (XPS) journal, October 2007

The structure of CO on Ni(111) journal, January 1982

H2 production for MC fuel cell by steam reforming of ethanol over MgO supported Pd, Rh, Ni and Co catalysts journal, October 2004

Ethanol steam reforming over Co-based catalysts: Role of oxygen mobility journal, January 2009

Thermal Chemistry of Iodomethane on Ni(110). 1. Clean and Hydrogen-Predosed Surfaces journal, October 2004

Methyl iodide thermal reactions when chemisorbed on nickel(100) surfaces journal, September 1992

Water Dissociation on CeO 2 (100) and CeO 2 (111) Thin Films journal, August 2012

Reforming of Oxygenates for H 2 Production: Correlating Reactivity of Ethylene Glycol and Ethanol on Pt(111) and Ni/Pt(111) with Surface d-Band Center journal, February 2006

IRAS study of the adsorption of CO on Ni(111): Interrelation between various bonding modes of chemisorbed CO journal, January 1988

Reduction Characteristics of Ceria under Ethanol Steam Reforming Conditions: Effect of the Particle Size journal, December 2013

Adsorption and Reaction of C 1 −C 3 Alcohols over CeO X (111) Thin Films journal, July 2010

Use of biofuels to produce hydrogen (reformation processes) journal, January 2008

Nickel Mg K α XPS Spectra from the Physical Electronics Model 5400 Spectrometer journal, July 1994

Water–Gas Shift and CO Methanation Reactions over Ni–CeO2(111) Catalysts journal, January 2011

The catalytic synthesis of hydrocarbons from H2/CO mixtures over the group VIII metals IV. The kinetic behavior of CO hydrogenation over Ni catalysts journal, July 1976

Reaction network of steam reforming of ethanol over Ni-based catalysts journal, July 2004

Influence of Hydroxyls on Pd Atom Mobility and Clustering on Rutile TiO 2 (011)-2 × 1 journal, May 2014

Support effects in cobalt-based ethanol steam reforming catalysts: Reaction of ethanol on Co/CeO2/YSZ(100) model catalysts journal, July 2012

Interplay between particle size, composition, and structure of MgAl2O4-supported Co–Cu catalysts and their influence on carbon accumulation during steam reforming of ethanol journal, November 2013

Efficient Production of Hydrogen over Supported Cobalt Catalysts from Ethanol Steam Reforming journal, July 2002

Interactions of alcohols with a nickel oxide(100) surface studied by high-resolution electron energy loss spectroscopy and temperature-programmed desorption spectroscopy journal, September 1993

Ethanol steam reforming over Ni and Ni–Cu catalysts journal, August 2009

The ethanol steam reforming over Cu-Ni/SiO2 catalysts: Effect of Cu/Ni ratio journal, August 2011

Interactions of Ni Nanoparticles with Reducible CeO 2 (111) Thin Films journal, April 2012

High Activity of Ce1−xNixO2−y for H2 Production through Ethanol Steam Reforming: Tuning Catalytic Performance through Metal-Oxide Interactions journal, November 2010

X-ray photoelectron spectroscopic study of magnetron sputtered carbon–nickel composite films journal, September 2008

Production of Hydrogen from Ethanol: Review of Reaction Mechanism and Catalyst Deactivation journal, April 2012

Hollow Fibers Networked with Perovskite Nanoparticles for H2 Production from Heavy Oil journal, October 2013

Mechanism of Ethanol Reforming: Theoretical Foundations journal, March 2009

Adsorption and reaction of methanol on thin-film cerium oxide journal, April 2006

A Study of the Thermal Reactions of Methyl Iodide Coadsorbed with Hydrogen on Ni(111) Surfaces: Hydrogenation of Methyl Species to Methane journal, June 1994

Theoretical Studies of the Adsorption of CO and C on Ni(111) and Ni/CeO 2 (111): Evidence of a Strong Metal–Support Interaction journal, April 2013

High-pressure catalytic reactions over single-crystal metal surfaces journal, November 1991

Electron spectroscopy of single crystal and polycrystalline cerium oxide surfaces journal, July 1998

In-situ FT-IRAS study of the CO oxidation reaction over Ru(001) journal, August 1991

Surface Defect Characterization in Oxygen-Dosed Nickel Surfaces and in NiO Thin Films by CO Adsorption−Desorption Experiments journal, October 1997

Superior performance of Ni–W–Ce mixed-metal oxide catalysts for ethanol steam reforming: Synergistic effects of W- and Ni-dopants journal, January 2015

Formation of metastable phases of Ni-C journal, September 1992

The Electronic Structure and Chemical Properties of a Ni/CeO 2 Anode in a Solid Oxide Fuel Cell: A DFT + U Study journal, November 2010

Correlation of Oxygen Storage Capacity and Structural Distortion in Transition-Metal-, Noble-Metal-, and Rare-Earth-Ion-Substituted CeO 2 from First Principles Calculation journal, September 2010

Effect of Ceria Support on the Structure of Ni Nanoparticles journal, April 2010

An STM study of carbon-induced structures on Ni(111): evidence for a carbidic-phase clock reconstruction journal, November 1995

The role of the catalytic particle in the growth of carbon nanotubes by plasma enhanced chemical vapor deposition journal, June 2004

The influence of nano-architectured CeO supports in RhPd/CeO2 for the catalytic ethanol steam reforming reaction journal, September 2015

Ordered cerium oxide thin films grown on Ru(0001) and Ni(111) journal, June 1999

In Situ and Theoretical Studies for the Dissociation of Water on an Active Ni/CeO 2 Catalyst: Importance of Strong Metal-Support Interactions for the Cleavage of O-H Bonds journal, February 2015

Effects of preparation mode and doping on the genesis and properties of Ni/Ce1-xMxOy nanocrystallites (M = Gd, La, Mg) for catalytic applications journal, January 2019

Ceria-based model catalysts: fundamental studies on the importance of the metal–ceria interface in CO oxidation, the water–gas shift, CO 2 hydrogenation, and methane and alcohol reforming journal, January 2017

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

Electronic Metal–Support Interactions and the Production of Hydrogen Through the Water-Gas Shift Reaction and Ethanol Steam Reforming: Fundamental Studies with Well-Defined Model Catalysts
journal, August 2013

Interaction of Methanol with Well-Defined Ceria Surfaces: Reflection/Absorption Infrared Spectroscopy, X-ray Photoelectron Spectroscopy, and Temperature-Programmed Desorption Study
journal, August 1999

Steam Reforming of Ethanol on Ni/CeO ₂ : Reaction Pathway and Interaction between Ni and the CeO ₂ Support
journal, April 2013

Adsorption and reaction of formaldehyde on thin-film cerium oxide
journal, April 2006

Tailoring the Properties of Atomic Layer Deposited Nickel and Nickel Carbide Thin Films via Chain-Length Control of the Alcohol Reducing Agents
journal, September 2014

The Unique Properties of the Oxide-Metal Interface: Reaction of Ethanol on an Inverse Model CeO _x –Au(111) Catalyst
journal, October 2014

Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering
journal, September 2006

Bond activation sequence observed in the chemisorption and surface reaction of ethanol on Ni(111)
journal, May 1986

Characterization of surface processes at the Ni-based catalyst during the methanation of biomass-derived synthesis gas: X-ray photoelectron spectroscopy (XPS)
journal, October 2007

The structure of CO on Ni(111)
journal, January 1982

H2 production for MC fuel cell by steam reforming of ethanol over MgO supported Pd, Rh, Ni and Co catalysts
journal, October 2004

Ethanol steam reforming over Co-based catalysts: Role of oxygen mobility
journal, January 2009

Thermal Chemistry of Iodomethane on Ni(110). 1. Clean and Hydrogen-Predosed Surfaces
journal, October 2004

Methyl iodide thermal reactions when chemisorbed on nickel(100) surfaces
journal, September 1992

Water Dissociation on CeO ₂ (100) and CeO ₂ (111) Thin Films
journal, August 2012

Reforming of Oxygenates for H ₂ Production: Correlating Reactivity of Ethylene Glycol and Ethanol on Pt(111) and Ni/Pt(111) with Surface d-Band Center
journal, February 2006

IRAS study of the adsorption of CO on Ni(111): Interrelation between various bonding modes of chemisorbed CO
journal, January 1988

Reduction Characteristics of Ceria under Ethanol Steam Reforming Conditions: Effect of the Particle Size
journal, December 2013

Adsorption and Reaction of C ₁ −C ₃ Alcohols over CeO _X (111) Thin Films
journal, July 2010

Use of biofuels to produce hydrogen (reformation processes)
journal, January 2008

Nickel Mg K _α XPS Spectra from the Physical Electronics Model 5400 Spectrometer
journal, July 1994

Water–Gas Shift and CO Methanation Reactions over Ni–CeO2(111) Catalysts
journal, January 2011

The catalytic synthesis of hydrocarbons from H2/CO mixtures over the group VIII metals IV. The kinetic behavior of CO hydrogenation over Ni catalysts
journal, July 1976

Reaction network of steam reforming of ethanol over Ni-based catalysts
journal, July 2004

Influence of Hydroxyls on Pd Atom Mobility and Clustering on Rutile TiO ₂ (011)-2 × 1
journal, May 2014

Support effects in cobalt-based ethanol steam reforming catalysts: Reaction of ethanol on Co/CeO2/YSZ(100) model catalysts
journal, July 2012

Interplay between particle size, composition, and structure of MgAl2O4-supported Co–Cu catalysts and their influence on carbon accumulation during steam reforming of ethanol
journal, November 2013

Efficient Production of Hydrogen over Supported Cobalt Catalysts from Ethanol Steam Reforming
journal, July 2002

Interactions of alcohols with a nickel oxide(100) surface studied by high-resolution electron energy loss spectroscopy and temperature-programmed desorption spectroscopy
journal, September 1993

Ethanol steam reforming over Ni and Ni–Cu catalysts
journal, August 2009

The ethanol steam reforming over Cu-Ni/SiO2 catalysts: Effect of Cu/Ni ratio
journal, August 2011

Interactions of Ni Nanoparticles with Reducible CeO ₂ (111) Thin Films
journal, April 2012

High Activity of Ce1−xNixO2−y for H2 Production through Ethanol Steam Reforming: Tuning Catalytic Performance through Metal-Oxide Interactions
journal, November 2010

X-ray photoelectron spectroscopic study of magnetron sputtered carbon–nickel composite films
journal, September 2008

Production of Hydrogen from Ethanol: Review of Reaction Mechanism and Catalyst Deactivation
journal, April 2012

Hollow Fibers Networked with Perovskite Nanoparticles for H2 Production from Heavy Oil
journal, October 2013

Mechanism of Ethanol Reforming: Theoretical Foundations
journal, March 2009

Adsorption and reaction of methanol on thin-film cerium oxide
journal, April 2006

A Study of the Thermal Reactions of Methyl Iodide Coadsorbed with Hydrogen on Ni(111) Surfaces: Hydrogenation of Methyl Species to Methane
journal, June 1994

Theoretical Studies of the Adsorption of CO and C on Ni(111) and Ni/CeO ₂ (111): Evidence of a Strong Metal–Support Interaction
journal, April 2013

High-pressure catalytic reactions over single-crystal metal surfaces
journal, November 1991

Electron spectroscopy of single crystal and polycrystalline cerium oxide surfaces
journal, July 1998

In-situ FT-IRAS study of the CO oxidation reaction over Ru(001)
journal, August 1991

Surface Defect Characterization in Oxygen-Dosed Nickel Surfaces and in NiO Thin Films by CO Adsorption−Desorption Experiments
journal, October 1997

Superior performance of Ni–W–Ce mixed-metal oxide catalysts for ethanol steam reforming: Synergistic effects of W- and Ni-dopants
journal, January 2015

Formation of metastable phases of Ni-C
journal, September 1992

The Electronic Structure and Chemical Properties of a Ni/CeO ₂ Anode in a Solid Oxide Fuel Cell: A DFT + U Study
journal, November 2010

Correlation of Oxygen Storage Capacity and Structural Distortion in Transition-Metal-, Noble-Metal-, and Rare-Earth-Ion-Substituted CeO ₂ from First Principles Calculation
journal, September 2010

Effect of Ceria Support on the Structure of Ni Nanoparticles
journal, April 2010

An STM study of carbon-induced structures on Ni(111): evidence for a carbidic-phase clock reconstruction
journal, November 1995

The role of the catalytic particle in the growth of carbon nanotubes by plasma enhanced chemical vapor deposition
journal, June 2004

The influence of nano-architectured CeO supports in RhPd/CeO2 for the catalytic ethanol steam reforming reaction
journal, September 2015

Ordered cerium oxide thin films grown on Ru(0001) and Ni(111)
journal, June 1999

In Situ and Theoretical Studies for the Dissociation of Water on an Active Ni/CeO ₂ Catalyst: Importance of Strong Metal-Support Interactions for the Cleavage of O-H Bonds
journal, February 2015

Effects of preparation mode and doping on the genesis and properties of Ni/Ce1-xMxOy nanocrystallites (M = Gd, La, Mg) for catalytic applications
journal, January 2019

Ceria-based model catalysts: fundamental studies on the importance of the metal–ceria interface in CO oxidation, the water–gas shift, CO ₂ hydrogenation, and methane and alcohol reforming
journal, January 2017