DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: A re-examination of the catalyst activation and temperature hysteresis in methane combustion on Pt/Al2O3

Abstract

Methane combustion is an industrially important reaction that has been extensively studied. Supported Pt catalysts on Al2O3 exhibit excellent activity in this reaction owing to their Csingle bondH bond activation capability. Pt/Al2O3 catalyst remains almost inactive until the conversion increases abruptly at the ignition temperature (Tign). The temperature hysteresis behavior has been reported, where after ignition, as the temperature is lowered below Tign, the catalyst continues to exhibit high activity. The activation has been previously attributed to the removal of adsorbed oxygen on Pt sites at Tign, while the hysteresis has been explained by the local temperature elevation caused by the reaction heat. Here in this work, this behavior was re-examined at a small scale in a fixed-bed flow reactor over a range of pre-treatment and reaction mixture conditions. Low-temperature activation was achieved by pre-treating the catalyst with CH4. Carefully designed control experiments yielded observations that cannot be rationalized by the existing theory, suggesting that it is incomplete. Based on these new results, we propose a more comprehensive theory describing the active sites in the oxidation reaction as methane-derived adsorbed carbon active sites, and their formation as the controlling factor in the catalyst activation. The hysteresis can be better explainedmore » by the enhanced stability of active sites under reaction conditions. In situ infrared spectroscopy and mass spectrometry studies were conducted in a flow cell, providing strong evidence supporting the theory. The dissociative adsorption of CH4 was studied under a variety of pre-treatment conditions, and proved to be responsible for the active site formation. The fundamental understanding obtained in this work contributes significant insights to the understanding of reaction mechanism.« less

Authors:
 [1];  [1];  [1]
  1. Indiana University, Bloomington, IN (United States)
Publication Date:
Research Org.:
Indiana Univ., Bloomington, IN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1537968
Alternate Identifier(s):
OSTI ID: 1495844
Grant/Contract Number:  
SC0016367
Resource Type:
Accepted Manuscript
Journal Name:
Applied Catalysis. A, General
Additional Journal Information:
Journal Volume: 549; Journal Issue: C; Journal ID: ISSN 0926-860X
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; methane oxidation; C-H activation; catalyst pretreatment; temperature hysteresis; flow reactor; DRIFTS-MS

Citation Formats

Chen, Linxiao, McCann, Joseph P., and Tait, Steven L.. A re-examination of the catalyst activation and temperature hysteresis in methane combustion on Pt/Al2O3. United States: N. p., 2017. Web. doi:10.1016/j.apcata.2017.09.008.
Chen, Linxiao, McCann, Joseph P., & Tait, Steven L.. A re-examination of the catalyst activation and temperature hysteresis in methane combustion on Pt/Al2O3. United States. https://doi.org/10.1016/j.apcata.2017.09.008
Chen, Linxiao, McCann, Joseph P., and Tait, Steven L.. Fri . "A re-examination of the catalyst activation and temperature hysteresis in methane combustion on Pt/Al2O3". United States. https://doi.org/10.1016/j.apcata.2017.09.008. https://www.osti.gov/servlets/purl/1537968.
@article{osti_1537968,
title = {A re-examination of the catalyst activation and temperature hysteresis in methane combustion on Pt/Al2O3},
author = {Chen, Linxiao and McCann, Joseph P. and Tait, Steven L.},
abstractNote = {Methane combustion is an industrially important reaction that has been extensively studied. Supported Pt catalysts on Al2O3 exhibit excellent activity in this reaction owing to their Csingle bondH bond activation capability. Pt/Al2O3 catalyst remains almost inactive until the conversion increases abruptly at the ignition temperature (Tign). The temperature hysteresis behavior has been reported, where after ignition, as the temperature is lowered below Tign, the catalyst continues to exhibit high activity. The activation has been previously attributed to the removal of adsorbed oxygen on Pt sites at Tign, while the hysteresis has been explained by the local temperature elevation caused by the reaction heat. Here in this work, this behavior was re-examined at a small scale in a fixed-bed flow reactor over a range of pre-treatment and reaction mixture conditions. Low-temperature activation was achieved by pre-treating the catalyst with CH4. Carefully designed control experiments yielded observations that cannot be rationalized by the existing theory, suggesting that it is incomplete. Based on these new results, we propose a more comprehensive theory describing the active sites in the oxidation reaction as methane-derived adsorbed carbon active sites, and their formation as the controlling factor in the catalyst activation. The hysteresis can be better explained by the enhanced stability of active sites under reaction conditions. In situ infrared spectroscopy and mass spectrometry studies were conducted in a flow cell, providing strong evidence supporting the theory. The dissociative adsorption of CH4 was studied under a variety of pre-treatment conditions, and proved to be responsible for the active site formation. The fundamental understanding obtained in this work contributes significant insights to the understanding of reaction mechanism.},
doi = {10.1016/j.apcata.2017.09.008},
journal = {Applied Catalysis. A, General},
number = C,
volume = 549,
place = {United States},
year = {Fri Sep 08 00:00:00 EDT 2017},
month = {Fri Sep 08 00:00:00 EDT 2017}
}

Journal Article:

Citation Metrics:
Cited by: 25 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Some aspects of hydrocarbon activation on platinum group metal combustion catalysts
journal, January 1996


High pressure methane catalytic combustion over novel partially coated LaMnO3-based monoliths
journal, January 2015

  • Barbato, Paola Sabrina; Di Sarli, Valeria; Landi, Gianluca
  • Chemical Engineering Journal, Vol. 259
  • DOI: 10.1016/j.cej.2014.07.123

Infrared study of CO adsorption on Pt–Rh/Al 2 O 3 catalysts
journal, January 1991

  • Anderson, James A.; Rochester, Colin H.
  • J. Chem. Soc., Faraday Trans., Vol. 87, Issue 9
  • DOI: 10.1039/FT9918701479

Carbon on Pt(111): Characterization and influence on the chemisorptive properties
journal, March 1986


Hysteresis phenomena in heterogeneous exothermal catalytic reactions and methods for decreasing the overheating of catalyst nanoclusters
journal, May 2015

  • Subbotin, Alexander N.; Subbotina, Irina R.; Golosman, Evgeny Z.
  • Mendeleev Communications, Vol. 25, Issue 3
  • DOI: 10.1016/j.mencom.2015.05.020

High-Pressure Methane Combustion over a Perovskyte Catalyst
journal, December 2011

  • Barbato, Paola S.; Di Benedetto, Almerinda; Di Sarli, Valeria
  • Industrial & Engineering Chemistry Research, Vol. 51, Issue 22
  • DOI: 10.1021/ie201736p

Anomalous steady-state and spatio-temporal features of methane oxidation on Pt/Pd/Al2O3 monolith spanning lean and rich conditions
journal, April 2015

  • Bugosh, Gregory S.; Easterling, Vencon G.; Rusakova, Irene A.
  • Applied Catalysis B: Environmental, Vol. 165
  • DOI: 10.1016/j.apcatb.2014.09.058

Electronic transfer and ligand effects in the infrared spectra of adsorbed carbon monoxide
journal, August 1984


Modelling and simulation of heterogeneous oxidation of methane on a platinum foil
journal, December 1994


Carbon monoxide oxidation under transient conditions: A fourier-transform infrared transmission spectroscopy study
journal, July 1985


Wrong-way behavior of packed-bed reactors: Influence of interphase transport
journal, July 1989


Temperature Fronts and Patterns in Catalytic Systems
journal, August 1997

  • Luss, Dan
  • Industrial & Engineering Chemistry Research, Vol. 36, Issue 8
  • DOI: 10.1021/ie960597k

Reactivity of Chemisorbed Oxygen Atoms and Their Catalytic Consequences during CH 4 –O 2 Catalysis on Supported Pt Clusters
journal, October 2011

  • Chin, Ya-Huei(Cathy); Buda, Corneliu; Neurock, Matthew
  • Journal of the American Chemical Society, Vol. 133, Issue 40
  • DOI: 10.1021/ja202411v

Stepped single-crystal surfaces as models for small catalyst particles
journal, April 1985


Role of the Interface between Pd and PdO in Methane Dissociation
journal, September 2011

  • Kinnunen, Niko M.; Hirvi, Janne T.; Suvanto, Mika
  • The Journal of Physical Chemistry C, Vol. 115, Issue 39
  • DOI: 10.1021/jp204360c

Metal dispersion of CeO2–ZrO2 supported platinum catalysts measured by H2 or CO chemisorption
journal, March 2004


Selectivity of chemisorbed oxygen in C–H bond activation and CO oxidation and kinetic consequences for CH4–O2 catalysis on Pt and Rh clusters
journal, October 2011


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

  • Chin, Ya-Huei (Cathy); Iglesia, Enrique
  • The Journal of Physical Chemistry C, Vol. 115, Issue 36
  • DOI: 10.1021/jp203324y

Dynamics of homogeneous-heterogeneous reactors
journal, June 1992


Spatially resolving concentration and temperature gradients during the oxidation of propylene on Pt/Al2O3
journal, August 2009


Oxidation of propylene over Pd(551): Temperature hysteresis induced by carbon deposition and oxygen adsorption
journal, April 2015


Catalytic Combustion of Methane over Pt–Ce Oxides under Scarce Oxygen Condition
journal, February 2016

  • Jin, Jianhui; Li, Chuang; Tsang, Chi-Wing
  • Industrial & Engineering Chemistry Research, Vol. 55, Issue 8
  • DOI: 10.1021/acs.iecr.5b04202

In situ infrared study of the catalytic ignition of methane on Pt/Al2O3
journal, April 2006


Influence of gas composition on activity and durability of bimetallic Pd-Pt/Al2O3 catalysts for total oxidation of methane
journal, December 2015

  • Gremminger, Andreas Thomas; Pereira de Carvalho, Hudson Wallace; Popescu, Radian
  • Catalysis Today, Vol. 258
  • DOI: 10.1016/j.cattod.2015.01.034

XAFS study of Pt/Al2O3 nanosystem with metal-oxide active component
journal, May 2009

  • Beck, I. E.; Kriventsov, V. V.; Ivanov, D. P.
  • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 603, Issue 1-2
  • DOI: 10.1016/j.nima.2008.12.170

In situ ATR-IR study of CO adsorption and oxidation over Pt/Al2O3 in gas and aqueous phase: Promotion effects by water and pH
journal, February 2007


Oxidative catalytic removal of hydrocarbons over Pt/Al2O3 catalysts
journal, November 2000


A transient in situ FTIR and XANES study of CO oxidation over Pt/AlO catalysts
journal, September 2004


Catalytic Behavior of Flame-Made Pd/TiO 2 Nanoparticles in Methane Oxidation at Low Temperatures
journal, August 2014

  • Niu, Fang; Li, Shuiqing; Zong, Yichen
  • The Journal of Physical Chemistry C, Vol. 118, Issue 33
  • DOI: 10.1021/jp504859d

A Study of Ethanol Reactions over Pt/CeO2 by Temperature-Programmed Desorption and in Situ FT-IR Spectroscopy: Evidence of Benzene Formation
journal, April 2000

  • Yee, Anna; Morrison, Scott J.; Idriss, Hicham
  • Journal of Catalysis, Vol. 191, Issue 1
  • DOI: 10.1006/jcat.1999.2765

Methane catalytic combustion under pressure
journal, December 2012


Study of CO oxidation on the (111) face of nickel during Ni−NiO phase transition
journal, June 1980

  • Kalinkin, A. V.; Boreskov, G. K.; Savchenko, V. I.
  • Reaction Kinetics and Catalysis Letters, Vol. 13, Issue 2
  • DOI: 10.1007/BF02074180

Methane oxidation over Pd and Pt studied by DFT and kinetic modeling
journal, October 2013


Investigation of Pt/Al2O3 and Pd/Al2O3 catalysts for the combustion of methane at low concentrations
journal, December 1994


High Selectivity for Primary C–H Bond Cleavage of Propane σ-Complexes on the PdO(101) Surface
journal, October 2011

  • Weaver, Jason F.; Hakanoglu, Can; Antony, Abbin
  • Journal of the American Chemical Society, Vol. 133, Issue 40
  • DOI: 10.1021/ja206599k

Ignition and extinction in the catalytic oxidation of hydrocarbons over platinum
journal, April 1996


Effect of the preparation procedure on the properties of three-way automotive platinum—rhodium/ alumina—ceria catalysts
journal, December 1994


The adsorption of oxygen on a stepped platinum single crystal surface
journal, August 1978


Consequences of Metal–Oxide Interconversion for C–H Bond Activation during CH 4 Reactions on Pd Catalysts
journal, October 2013

  • Chin, Ya-Huei (Cathy); Buda, Corneliu; Neurock, Matthew
  • Journal of the American Chemical Society, Vol. 135, Issue 41
  • DOI: 10.1021/ja405004m

FT-IR study of CO adsorption on Pt/CeO2: characterisation and structural rearrangement of small Pt particles
journal, January 2005

  • Bazin, P.; Saur, O.; Lavalley, J. C.
  • Physical Chemistry Chemical Physics, Vol. 7, Issue 1
  • DOI: 10.1039/b414159h

Insight into the structure of supported palladium catalysts during the total oxidation of methane
journal, January 2007

  • Grunwaldt, Jan-Dierk; Vegten, Niels van; Baiker, Alfons
  • Chemical Communications, Issue 44
  • DOI: 10.1039/b710222d

Effect of platinum dispersion on the catalytic activity of Pt/Al2O3 for the oxidation of carbon monoxide and propene
journal, October 2013


Selective catalytic oxidation of CO in H2: structural study of Fe oxide-promoted Pt/alumina catalyst
journal, March 2002


Coupled harmonic oscillator models of carbon monoxide adsorbed on stepped, platinum surfaces
journal, January 1987


Spatially resolved temperature and gas species concentration changes during C3H6 oxidation over a Pt/Al2O3 catalyst following sulfur exposure
journal, April 2011


Numerical Studies of Methane Catalytic Combustion Inside a Monolith Honeycomb Reactor Using Multi-Step Surface Reactions
journal, January 2000

  • Chou, Chen-Pang; Chen, Jyh-Yuan; Evans, Greg H.
  • Combustion Science and Technology, Vol. 150, Issue 1-6
  • DOI: 10.1080/00102200008952116

Structure sensitivity of methane oxidation over platinum and palladium
journal, April 1990


Characterisation of Model Three-Way Catalysts
journal, August 1998

  • Lévy, P. J.; Pitchon, V.; Perrichon, V.
  • Journal of Catalysis, Vol. 178, Issue 1
  • DOI: 10.1006/jcat.1998.2150

An infrared study of the adsorption of CO on a stepped platinum surface
journal, January 1985


Evaluating the Effects of Precious Metal Distribution along a Monolith-Supported Catalyst for CO oxidation
journal, May 2012

  • Al-Adwani, Suad M.; Soares, Joao; Epling, William S.
  • Industrial & Engineering Chemistry Research, Vol. 51, Issue 19
  • DOI: 10.1021/ie202969u

Taking advantage of hysteresis in methane partial oxidation over Pt on honeycomb monolith
journal, December 2011


Alumina-supported platinum catalysts: Local atomic structure and catalytic activity for complete methane oxidation
journal, September 2014

  • Pakharukova, Vera P.; Pakharukov, Ilya Yu.; Bukhtiyarov, Valerii I.
  • Applied Catalysis A: General, Vol. 486
  • DOI: 10.1016/j.apcata.2014.08.014

The stoichiometry of hydrogen-oxygen titrations on supported platinum catalysts
journal, May 1978


The stoichiometry for hydrogen titration of oxygen on supported platinum
journal, October 1967


Combustion of Methane over Palladium-Based Catalysts: Catalytic Deactivation and Role of the Support
journal, April 2012

  • Schwartz, William R.; Ciuparu, Dragos; Pfefferle, Lisa D.
  • The Journal of Physical Chemistry C, Vol. 116, Issue 15
  • DOI: 10.1021/jp212236e

Methane oxidation hysteresis over Pt/Al2O3
journal, May 2014


Improved CO, hydrocarbon and NO oxidation performance using zone-coated Pt-based catalysts
journal, May 2013


Dynamics and Thermodynamics of Pd–PdO Phase Transitions: Effects of Pd Cluster Size and Kinetic Implications for Catalytic Methane Combustion
journal, January 2016

  • Chin, Ya-Huei (Cathy); García-Diéguez, Mónica; Iglesia, Enrique
  • The Journal of Physical Chemistry C, Vol. 120, Issue 3
  • DOI: 10.1021/acs.jpcc.5b06677

Surface interaction in the platinum-.gamma.-alumina system. V. Effects of atmosphere and fractal topology on the sintering of platinum
journal, September 1986

  • Rothschild, Walter G.; Yao, H. C.; Plummer, H. K.
  • Langmuir, Vol. 2, Issue 5
  • DOI: 10.1021/la00071a010

Hydrogen-oxygen titration method for the measurement of supported platinum surface areas
journal, December 1965


Inverse Hysteresis Phenomena During CO and C3H6 Oxidation over a Pt/Al2O3 Catalyst
journal, July 2012


Platinum nanoparticles on Al2O3: Correlation between the particle size and activity in total methane oxidation
journal, November 2009

  • Beck, Irene E.; Bukhtiyarov, Valerii I.; Pakharukov, Ilya Yu.
  • Journal of Catalysis, Vol. 268, Issue 1
  • DOI: 10.1016/j.jcat.2009.09.001

Methane oxidation over alumina supported platinum investigated by time-resolved in situ XANES spectroscopy
journal, November 2007


Works referencing / citing this record: