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Title: Infrared reflection absorption spectroscopy and temperature-programmed desorption studies of CO adsorption on Ni/CeO2(111) thin films: The role of the ceria support

Journal Article · · Journal of Vacuum Science and Technology A
DOI:https://doi.org/10.1116/6.0001409· OSTI ID:1839209

Ceria-supported Ni has shown unique catalytic activity due to unique properties of small Ni particles and strong metal-support interaction. Identification of adsorption sites and understanding the chemical interaction over Ni-ceria at the fundamental level provide crucial insights into the reaction pathways of complex catalytic processes. In this study, to probe the surface sites, the adsorption of CO was carried out with model Ni/ceria systems consisting of Ni nanoparticles vapor-deposited on well-ordered CeOx(111) (1.5 < x < 2) thin films using infrared reflection absorption spectroscopy (IRRAS) and temperature-programmed desorption (TPD) under ultrahigh vacuum (UHV) conditions. Fully oxidized CeO2(111) (Ce4+) and partially reduced CeO1.75(111) (Ce4+/Ce3+) thin films were grown on Ru(0001) to examine the role of the ceria support. Additionally, Ni with low coverages (e.g., 0.2 ML) grows forming small two-dimensional particles on ceria at 300 K, which develop into three-dimensional clusters after heating to 700 K. In the absence of Ni, CO adsorption at 1 mTorr at 100 K shows distinct IR bands at 2158 cm-1 on CeO2 and 2165 cm-1 on CeO1.75. Bridging and atop IR bands associated with CO adsorption over metallic Ni were observed on the Ni-CeO1.75 surface at 300 K under UHV conditions. CO adsorption over Ni0 was also observed over as-deposited Ni on CeO2. However, a new IR band at 2146 cm-1 due to CO adsorption over Ni2+ species was detected at 100 K over the annealed Ni particles on CeO2. CO IRRAS data suggest the oxidation of Ni to Ni2+ on CeO2 and the formation of predominant Ni2+ species with heating, which is further confirmed with CO TPD data and previous x-ray photoelectron spectroscopy results.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); National Aeronautics and Space Administration (NASA)
Grant/Contract Number:
SC0012704; CHE 1151846; NNX15AI08H
OSTI ID:
1839209
Alternate ID(s):
OSTI ID: 1994455
Report Number(s):
BNL-222558-2021-JAAM
Journal Information:
Journal of Vacuum Science and Technology A, Vol. 40, Issue 1; ISSN 0734-2101
Publisher:
American Vacuum Society / AIPCopyright Statement
Country of Publication:
United States
Language:
English

References (51)

Ceria-Based Materials in Hydrogenation and Reforming Reactions for CO2 Valorization journal February 2019
Insight into Ni/Ce1−xZrxO2−δ support interplay for enhanced methane steam reforming journal February 2019
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 journal January 2016
Dry Reforming of Methane on a Highly-Active Ni-CeO 2 Catalyst: Effects of Metal-Support Interactions on C−H Bond Breaking journal May 2016
A review on reforming bio-ethanol for hydrogen production journal October 2007
Renewable Hydrogen from Ethanol by Autothermal Reforming journal February 2004
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
Water–Gas Shift and CO Methanation Reactions over Ni–CeO2(111) Catalysts journal January 2011
Four challenges for nickel steam-reforming catalysts journal January 2006
A theoretical study of CH 4 dissociation on pure and gold‐alloyed Ni(111) surfaces journal October 1996
A review on catalyst development for dry reforming of methane to syngas: Recent advances journal July 2019
Progress in Synthesis of Highly Active and Stable Nickel-Based Catalysts for Carbon Dioxide Reforming of Methane journal October 2015
Room-Temperature Activation of Methane and Dry Re-forming with CO 2 on Ni-CeO 2 (111) Surfaces: Effect of Ce 3+ Sites and Metal–Support Interactions on C–H Bond Cleavage journal November 2016
Ceria Maintains Smaller Metal Catalyst Particles by Strong Metal-Support Bonding journal August 2010
Nature of the Active Sites on Ni/CeO 2 Catalysts for Methane Conversions journal August 2021
Effect of Ceria Support on the Structure of Ni Nanoparticles journal April 2010
Reaction Pathway for Coke-Free Methane Steam Reforming on a Ni/CeO 2 Catalyst: Active Sites and the Role of Metal–Support Interactions journal June 2021
Catalytic Properties of Ceria and CeO 2 -Containing Materials journal November 1996
Structure and surface properties of ceria-modified Ni-based catalysts for hydrogen production journal June 2018
Methane Activation at the Metal–Support Interface of Ni 4 –CeO 2 (111) Catalyst: A Theoretical Study journal March 2019
Interactions of Ni Nanoparticles with Reducible CeO 2 (111) Thin Films journal April 2012
Growth of Pt Nanoparticles on Reducible CeO 2 (111) Thin Films: Effect of Nanostructures and Redox Properties of Ceria journal June 2010
Ni Nanoparticles on CeO 2 (111): Energetics, Electron Transfer, and Structure by Ni Adsorption Calorimetry, Spectroscopies, and Density Functional Theory journal April 2020
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
Reduction property and catalytic activity of Ce1−XNiXO2 mixed oxide catalysts for CH4 oxidation journal June 2003
Vibrational excitations and structure of CO adsorbed on Ni(100) journal January 1977
Adsorption of CO on a Ni(111) surface journal June 1974
Adsorption of carbon monoxide on nickel journal June 1977
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
The adsorption sites of CO on Ni(111) as determined by infrared reflection-absorption spectroscopy journal April 1979
An infrared reflection-absorption study of CO chemisorbed on clean and sulfided Ni(111) — Evidence for local surface interactions journal July 1985
Infrared Study of Adsorbed Molecules on Metal Surfaces by Reflection Techniques journal January 1966
Chemical activity of oxygen vacancies on ceria: a combined experimental and theoretical study on CeO 2 (111) journal January 2014
Vibrational Frequencies of Cerium-Oxide-Bound CO: A Challenge for Conventional DFT Methods journal December 2020
Morphology and chemical states of Ni supported on Ti-modified CeOx(111) interfaces journal September 2020
Ordered cerium oxide thin films grown on Ru(0001) and Ni(111) journal June 1999
Electron spectroscopy of single crystal and polycrystalline cerium oxide surfaces journal July 1998
Morphology of size-selected Pt n clusters on CeO 2 (111) journal March 2018
Growth, sintering, and chemical states of Co supported on reducible CeO2(111) thin films: The effects of the metal coverage and the nature of the support journal January 2021
Low Pressure RAIRS Studies of Model Catalytic Systems journal March 2010
Structural and Catalytic Properties of Model Supported Nickel Catalysts journal January 1994
Influence of alloyed Sn atoms on the chemisorption properties of Ni(111) as probed by RAIRS and TPD studies of CO adsorption journal April 1995
IRAS study of the adsorption of CO on Ni(111): Interrelation between various bonding modes of chemisorbed CO journal January 1988
CO adsorption on nanoislands: Ni on Au(111) journal June 2018
Adsorption of CO at Ni(100) surfaces: a FTIRAS - TDS study journal December 1992
The C=O stretching vibration of CO on Ni(100) by infrared emission spectroscopy journal May 1984
Infrared study of CO on NiO(100)
  • Vesecky, Scott M.; Xu, Xueping; Goodman, D. Wayne
  • Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 12, Issue 4 https://doi.org/10.1116/1.579146
journal July 1994
The structure of CO on Ni(111) journal January 1982
Surface Defect Characterization in Oxygen-Dosed Nickel Surfaces and in NiO Thin Films by CO Adsorption−Desorption Experiments journal October 1997
Size-Dependent Molecular Dissociation on Mass-Selected, Supported Metal Clusters journal September 1998
The surface chemistry of cerium oxide journal March 2015