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 »
- Authors:
-
- 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:
- Journal Article: 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. 2017.
"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},
url = {https://www.osti.gov/biblio/1537968},
journal = {Applied Catalysis. A, General},
issn = {0926-860X},
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}
}
Web of Science
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Works referencing / citing this record:
Synthesis of a Highly Stable Pd@CeO 2 Catalyst for Methane Combustion with the Synergistic Effect of Urea and Citric Acid
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