skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Dynamic Oxygen on Surface: Catalytic Intermediate and Coking Barrier in the Modeled CO2 Reforming of CH4 on Ni (111)

Journal Article · · ACS Catalysis
 [1];  [2];  [3];  [4];  [5];  [6];  [3];  [5];  [7];  [8]
  1. National Univ. of Singapore (Singapore). Dept. of Physics; Singapore-Peking Univ. Research Center for a Sustainable Low-Carbon Future (Singapore)
  2. Singapore-Peking Univ. Research Center for a Sustainable Low-Carbon Future (Singapore); Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
  3. Singapore-Peking Univ. Research Center for a Sustainable Low-Carbon Future (Singapore); National Univ. of Singapore (Singapore). Dept. of Chemistry
  4. Singapore-Peking Univ. Research Center for a Sustainable Low-Carbon Future (Singapore)
  5. Yale-NUS College (Singapore). Science Division; Princeton Univ., NJ (United States). Dept. of Chemistry
  6. Singapore-Peking Univ. Research Center for a Sustainable Low-Carbon Future (Singapore); Peking Univ., Beijing (China). College of Chemistry and Molecular Engineering
  7. Shanghai Normal Univ., Shanghai (China). Chinese Education Ministry Key Lab. of Resource Chemistry
  8. National Univ. of Singapore (Singapore). Dept. of Physics; Singapore-Peking Univ. Research Center for a Sustainable Low-Carbon Future (Singapore); National Univ. of Singapore (Singapore). Dept. of Chemistry; National Univ. of Singapore Suzhou Research Inst., Suzhou, (China)
+ Show Author Affiliations

We identify Ni-O phases as important intermediates in a model dry (CO2) reforming of methane catalyzed by Ni (111), based on results from in operando near ambient X-ray photoelectron spectroscopy (NAP-XPS), low energy electron diffraction (LEED) and scanning tunneling microscopy (STM). We find that under a CO2 or CO2-CH4 atmosphere, the Ni-O phases exist as p(2×2) structured chemisorbed oxygen (Chem-O), epitaxial NiO (111), or oxygen-rich NixOy (x2O3), depending on the chemical potential. The growth rates of the Ni-O phases have a negative correlation with temperature from 600 K to 900 K, proving that their dynamic concentrations in the reaction are not limited by CO2 activation, but by their thermal stability. Between 300 K and 800 K (1:1 CH4 and CO2 mixture), oxidation by CO2is dominant, resulting in a fully Ni-O covered surface. Between 800 K and 900 K, a partially oxidized Ni (111) exists which could greatly facilitate the effective conversion of CH4. As CH4 is activation-limited and dissociates mainly on metallic nickel, the released carbon species can quickly react with the adjacent oxygen (Ni-O phases) to form CO. After combining with carbon and releasing CO molecules, the Ni-O phases can be further regenerated through oxidation by CO2. In this way, the Ni-O phases participate in the catalytic process, acting as an intermediate in addition to the previously reported Ni-C phases. We also reveal the carbon phobic property of the Ni-O phases, which links to the intrinsic coking resistance of the catalysts. The low dynamic coverage of surface oxygen at higher temperatures (>900 K) is inferred to be an underlying factor causing carbon aggregation. Therefore solutions based on Ni-O stabilization are proposed in developing coking resisting catalysts.

Research Organization:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Singapore National Research Foundation
Grant/Contract Number:
SC00112704; R143-000-542-112
OSTI ID:
1336228
Report Number(s):
BNL-113260-2016-JA; R&D Project: 16083/16083; KC0403020
Journal Information:
ACS Catalysis, Vol. 6, Issue 7; ISSN 2155-5435
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 74 works
Citation information provided by
Web of Science

References (85)

The Fischer–Tropsch process: 1950–2000 journal January 2002
Bi-reforming of Methane from Any Source with Steam and Carbon Dioxide Exclusively to Metgas (CO–2H 2 ) for Methanol and Hydrocarbon Synthesis journal December 2012
Single Step Bi-reforming and Oxidative Bi-reforming of Methane (Natural Gas) with Steam and Carbon Dioxide to Metgas (CO-2H 2 ) for Methanol Synthesis: Self-Sufficient Effective and Exclusive Oxygenation of Methane to Methanol with Oxygen journal June 2015
Recycling of carbon dioxide to methanol and derived products – closing the loop journal January 2014
Reactivity of Chemisorbed Oxygen Atoms and Their Catalytic Consequences during CH 4 –O 2 Catalysis on Supported Pt Clusters journal October 2011
Xps study of chemisorption of CH4 on Ni(100) journal March 1990
Molecular beam study of dissociative sticking of methane on Ni(100) journal May 1995
Dissociative chemisorption of CH 4 on Ni(111) journal April 1992
Theoretical Studies of Stability and Reactivity of CHx Species on Ni(111) journal January 2000
Chemisorption of Methane on Ni(100) and Ni(111) Surfaces with Preadsorbed Potassium journal October 1999
Methane activation on Ni(111): Effects of poisons and step defects journal October 2005
Interaction of methane with Ni(111) and Ni(100); diffusion of carbon into nickel through the (100) surface; An aes-leed study journal August 1979
Kinetic Study of the Carbon Filament Formation by Methane Cracking on a Nickel Catalyst journal July 1997
CH4 dissociation on NiM(111) (M=Co, Rh, Ir) surface: A first-principles study journal November 2013
Carbon dioxide reforming of methane over ordered mesoporous NiO–Al2O3 composite oxides journal January 2011
A review of dry (CO 2 ) reforming of methane over noble metal catalysts journal January 2014
Progresses in the Preparation of Coke Resistant Ni-based Catalyst for Steam and CO2 Reforming of Methane journal February 2011
Progress in Synthesis of Highly Active and Stable Nickel-Based Catalysts for Carbon Dioxide Reforming of Methane journal October 2015
Coke Formation over a Nickel Catalyst under Methane Dry Reforming Conditions:  Thermodynamic and Kinetic Models journal July 2005
Mechanistic aspects of the dry reforming of methane over ruthenium catalysts journal August 2000
One-Pot Synthesis of Ordered Mesoporous NiO–CaO–Al 2 O 3 Composite Oxides for Catalyzing CO 2 Reforming of CH 4 journal May 2012
Carbon dioxide reforming of methane over ordered mesoporous NiO–MgO–Al2O3 composite oxides journal October 2011
Readsorption and Adsorption-Assisted Desorption of CO 2 on Basic Solids journal January 1998
CO 2 Reforming of CH 4 on Ni(111):  A Density Functional Theory Calculation journal May 2006
Transient study of the dry reforming of methane over Pt supported on different γ-Al2O3 journal January 2010
Improved activity of Ni/MgAl 2 O 4 for CO 2 methanation by the plasma decomposition journal September 2015
Insights into the mechanisms of CO2 methanation on Ni(111) surfaces by density functional theory journal October 2015
Complete Photocatalytic Reduction of CO 2 to Methane by H 2 under Solar Light Irradiation journal April 2014
The nature of the active site in heterogeneous metal catalysis journal January 2008
The photochemistry of CH4 adsorbed on Pt(1 1 1) studied by high resolution fast XPS journal June 2001
Carbon Dioxide Hydrogenation on Ni(110) journal July 2008
Orientation-Dependent Interaction between CO 2 Molecules Adsorbed on Ru(0001) journal April 2015
Photoelectron spectroscopy under ambient pressure and temperature conditions
  • Frank Ogletree, D.; Bluhm, Hendrik; Hebenstreit, Eleonore D.
  • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 601, Issue 1-2 https://doi.org/10.1016/j.nima.2008.12.155
journal March 2009
Reaction-Driven Restructuring of Rh-Pd and Pt-Pd Core-Shell Nanoparticles journal November 2008
Competitive Coadsorption of CO 2 with H 2 O, NH 3 , SO 2 , NO, NO 2 , N 2 , O 2 , and CH 4 in M-MOF-74 (M = Mg, Co, Ni): The Role of Hydrogen Bonding journal March 2015
Atom-Resolved Imaging of Dynamic Shape Changes in Supported Copper Nanocrystals journal March 2002
A Reactive Oxide Overlayer on Rhodium Nanoparticles during CO Oxidation and Its Size Dependence Studied by In Situ Ambient-Pressure X-ray Photoelectron Spectroscopy journal November 2008
Evolution of Structure and Chemistry of Bimetallic Nanoparticle Catalysts under Reaction Conditions journal June 2010
Effect of Catalyst Structure on Growth and Reactivity of Carbon Nanofibers over Ni/MgAl 2 O 4 journal June 2013
Structure and reactivity of plasma treated Ni/Al2O3 catalyst for CO2 reforming of methane journal May 2008
Preparation and characterization of coke resistant Ni/SiO2 catalyst for carbon dioxide reforming of methane journal January 2008
Molybdenum Carbide as Alternative Catalysts to Precious Metals for Highly Selective Reduction of CO 2 to CO journal May 2014
Catalyst Chemical State during CO Oxidation Reaction on Cu(111) Studied with Ambient-Pressure X-ray Photoelectron Spectroscopy and Near Edge X-ray Adsorption Fine Structure Spectroscopy journal August 2015
Final states after Ni2p photoemission in the nickel—oxygen system journal January 1991
Characterization of NiO by XPS journal July 1994
Chemisorption of oxygen on Ni(100) by SIMS and XPS journal November 1978
Does CO 2 dissociatively adsorb on Cu surfaces? journal October 1989
In Situ Oxidation Study of Pt(110) and Its Interaction with CO journal December 2011
Importance of the Metal-Oxide Interface in Catalysis: In Situ Studies of the Water-Gas Shift Reaction by Ambient-Pressure X-ray Photoelectron Spectroscopy journal April 2013
Highly active copper-ceria and copper-ceria-titania catalysts for methanol synthesis from CO2 journal July 2014
Adsorption of CO on clean and oxygen covered Ni(111) surfaces journal July 1976
Oxygen on Ni(111): A multiple-scattering analysis of the near-edge x-ray-absorption fine structure journal April 1990
A LEED analysis for the Ni(111)−(2 × 2)−O surface structure: Evidence for oxygen-induced relaxations of both vertical and lateral types in the close packed surface layer of nickel journal June 1990
Critical scattering at a marginally first order phase transition in two dimensions: the order-disorder transition of O/Ni(111)-p(2 × 2) journal April 1994
LEED study of the order-disorder transition of the p(2 × 2) phase of oxygen chemisorbed on Ni(111) journal April 1995
New setup for in situ x-ray photoelectron spectroscopy from ultrahigh vacuum to 1mbar journal January 2005
Near ambient pressure XPS investigation of the interaction of ethanol with Co/CeO2(111) journal November 2013
The Electronic Factor in Alkane Oxidation Catalysis journal January 2015
Promoter Effect of Early Stage Grown Surface Oxides: A Near-Ambient-Pressure XPS Study of CO Oxidation on PtSn Bimetallics journal December 2012
Direct Work Function Measurement by Gas Phase Photoelectron Spectroscopy and Its Application on PbS Nanoparticles journal November 2013
Local decomposition of NiO ultra-thin films formed on Ni(111) journal August 1998
Chemical changes in secondary electron emission during oxidation of nickel (100) and (111) crystal surfaces journal March 1975
Real time scanning tunneling microscopy study of the initial stages of oxidation of Ni(111) between 400 and 470 K
  • Hildebrandt, S.; Hagendorf, Ch.; Doege, T.
  • Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 18, Issue 3 https://doi.org/10.1116/1.582292
journal May 2000
Hydrogen effects on the electronic and microstructural properties of Ce, Ni, and CeNi2 intermetallic compound journal May 1994
Mechanism of low temperature decomposition of NiO single crystals journal September 2009
A study of thermal decomposition of sputtered NiO films journal October 2011
Catalytic activities and coking resistance of Ni/perovskites in steam reforming of methane journal May 2005
Long-Term Passivation of Strongly Interacting Metals with Single-Layer Graphene journal November 2015
Coking on nickel catalysts for steam reforming of hydrocarbons journal May 1974
Reactivity of Carbon Dioxide on Nickel: Role of CO in the Competing Interplay between Oxygen and Graphene journal May 2014
The formation and decomposition of nickel carbide in evaporated nickel films on graphite journal August 1978
Nickel Carbide as a Source of Grain Rotation in Epitaxial Graphene journal March 2012
Consequences of Metal–Oxide Interconversion for C–H Bond Activation during CH 4 Reactions on Pd Catalysts journal October 2013
Effects of Potassium on Ni−K/Al 2 O 3 Catalysts in the Synthesis of Carbon Nanofibers by Catalytic Hydrogenation of CO 2 journal August 2009
Atomic-Scale Structure and Catalytic Reactivity of the RuO2(110) Surface journal February 2000
Elementary Steps, the Role of Chemisorbed Oxygen, and the Effects of Cluster Size in Catalytic CH 4 –O 2 Reactions on Palladium journal August 2011
In Situ Observation of Surface Species on Iridium Oxide Nanoparticles during the Oxygen Evolution Reaction journal May 2014
Structure and Chemical State of the Pt(557) Surface during Hydrogen Oxidation Reaction Studied by in Situ Scanning Tunneling Microscopy and X-ray Photoelectron Spectroscopy journal August 2013
Active Surface Carbon—A Reactive Intermediate in the Production of Synthesis Gas from Methane and Carbon Dioxide journal September 1994
Nanophase Transition Metal Oxides Show Large Thermodynamically Driven Shifts in Oxidation-Reduction Equilibria journal October 2010
CO-Induced Embedding of Pt Adatoms in a Partially Reduced FeO x Film on Pt(111) journal July 2011
Evidence of Highly Active Cobalt Oxide Catalyst for the Fischer–Tropsch Synthesis and CO 2 Hydrogenation journal January 2014
Synergetic Effect of Surface and Subsurface Ni Species at Pt−Ni Bimetallic Catalysts for CO Oxidation journal February 2011
High-pressure X-ray photoelectron spectroscopy of palladium model hydrogenation catalysts.Part 1: Effect of gas ambient and temperature journal February 2005
Methane Oxidation on Pd(111):  In Situ XPS Identification of Active Phase journal June 2007

Cited By (5)

Influence of Solid Solution Formation on the Activity of CeO2 Supported Ni–Cu Mixed Oxide Catalysts in Dry Reforming of Methane journal May 2019
A Nickel-Based Perovskite Catalyst with a Bimodal Size Distribution of Nickel Particles for Dry Reforming of Methane journal March 2018
Lewis Acid Sites Stabilized Nickel Catalysts for Dry (CO 2 ) Reforming of Methane journal November 2016
Catalytic Intermediates of CO 2 Hydrogenation on Cu(111) Probed by In Operando Near-Ambient Pressure Technique journal October 2018
The Effect of CeO2 Preparation Method on the Carbon Pathways in the Dry Reforming of Methane on Ni/CeO2 Studied by Transient Techniques journal July 2019

Similar Records

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
36 MATERIALS SCIENCE
carbon dioxide
coking
dry reforming
methane
NAP-XPS
nickel
surface oxygen