Tuning Selectivity in the Direct Conversion of Methane to Methanol: Bimetallic Synergistic Effects on the Cleavage of C–H and O–H Bonds over NiCu/CeO 2 Catalysts
Abstract
The efficient activation of methane and the simultaneous water dissociation are crucial in many catalytic reactions on oxide-supported transition metal catalysts. On very low-loaded Ni/CeO2 surfaces, methane easily fully decomposes, CH4 → C + 4H, and water dissociates, H2O→ OH + H. However, in important reactions such as the direct oxidation of methane to methanol (MTM), where complex interplay exists between reactants (CH4, O2), it is desirable to avoid the complete dehydrogenation of methane to carbon. Remarkably, the barrier for the activation of C–H bonds in CHx (x = 1–3) species on Ni/CeO2 surfaces can be manipulated by adding Cu, forming bimetallic NiCu clusters, whereas the ease for cleavage of O–H bonds in water is not affected by ensemble effects, as obtained from density functional theory-based calculations. CH4 activation occurs only on Ni sites, and H2O activation occurs on both Ni and Cu sites. The MTM reaction pathway for the example of the Ni3Cu1/CeO2 model catalyst predicts a higher selectivity and a lower activation barrier for methanol production, compared with that for Ni4/CeO2. These findings point toward a possible strategy to design active and stable catalysts which can be employed for methane activation and conversions.
- Authors:
-
[1];
[2];
[2];
[3]
- Instituto de Catálisis y Petroleoquímica, CSIC, C/Marie Curie 2, 28049 Madrid, Spain, Instituto de Fisica Rosario (IFIR), CONICET-UNR, Bv. 27 de Febrero 210bis, 2000EZP Rosario, Santa Fe, Argentina
- Chemistry Division, Brookhaven National Laboratory, Upton, New York 11973, United States
- Instituto de Catálisis y Petroleoquímica, CSIC, C/Marie Curie 2, 28049 Madrid, Spain
- Publication Date:
- Research Org.:
- Inst. de Catálisis y Petroleoquímica, Madrid (Spain); Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); European Union’s Horizon 2020; Marie Skłodowska-Curie; MICINN-Spain
- OSTI Identifier:
- 1872499
- Alternate Identifier(s):
- OSTI ID: 1873661; OSTI ID: 1879423
- Report Number(s):
- BNL-223194-2022-JAAM
Journal ID: ISSN 1948-7185
- Grant/Contract Number:
- SC0019360; SC0012704
- Resource Type:
- Published Article
- Journal Name:
- Journal of Physical Chemistry Letters
- Additional Journal Information:
- Journal Name: Journal of Physical Chemistry Letters Journal Volume: 13 Journal Issue: 24; Journal ID: ISSN 1948-7185
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Bimetals; Catalysts; Hydrocarbons; Metal clusters; Organic reactions; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; Methane
Citation Formats
Lustemberg, Pablo G., Senanayake, Sanjaya D., Rodriguez, José A., and Ganduglia-Pirovano, M. Verónica. Tuning Selectivity in the Direct Conversion of Methane to Methanol: Bimetallic Synergistic Effects on the Cleavage of C–H and O–H Bonds over NiCu/CeO 2 Catalysts. United States: N. p., 2022.
Web. doi:10.1021/acs.jpclett.2c00885.
Lustemberg, Pablo G., Senanayake, Sanjaya D., Rodriguez, José A., & Ganduglia-Pirovano, M. Verónica. Tuning Selectivity in the Direct Conversion of Methane to Methanol: Bimetallic Synergistic Effects on the Cleavage of C–H and O–H Bonds over NiCu/CeO 2 Catalysts. United States. https://doi.org/10.1021/acs.jpclett.2c00885
Lustemberg, Pablo G., Senanayake, Sanjaya D., Rodriguez, José A., and Ganduglia-Pirovano, M. Verónica. Tue .
"Tuning Selectivity in the Direct Conversion of Methane to Methanol: Bimetallic Synergistic Effects on the Cleavage of C–H and O–H Bonds over NiCu/CeO 2 Catalysts". United States. https://doi.org/10.1021/acs.jpclett.2c00885.
@article{osti_1872499,
title = {Tuning Selectivity in the Direct Conversion of Methane to Methanol: Bimetallic Synergistic Effects on the Cleavage of C–H and O–H Bonds over NiCu/CeO 2 Catalysts},
author = {Lustemberg, Pablo G. and Senanayake, Sanjaya D. and Rodriguez, José A. and Ganduglia-Pirovano, M. Verónica},
abstractNote = {The efficient activation of methane and the simultaneous water dissociation are crucial in many catalytic reactions on oxide-supported transition metal catalysts. On very low-loaded Ni/CeO2 surfaces, methane easily fully decomposes, CH4 → C + 4H, and water dissociates, H2O→ OH + H. However, in important reactions such as the direct oxidation of methane to methanol (MTM), where complex interplay exists between reactants (CH4, O2), it is desirable to avoid the complete dehydrogenation of methane to carbon. Remarkably, the barrier for the activation of C–H bonds in CHx (x = 1–3) species on Ni/CeO2 surfaces can be manipulated by adding Cu, forming bimetallic NiCu clusters, whereas the ease for cleavage of O–H bonds in water is not affected by ensemble effects, as obtained from density functional theory-based calculations. CH4 activation occurs only on Ni sites, and H2O activation occurs on both Ni and Cu sites. The MTM reaction pathway for the example of the Ni3Cu1/CeO2 model catalyst predicts a higher selectivity and a lower activation barrier for methanol production, compared with that for Ni4/CeO2. These findings point toward a possible strategy to design active and stable catalysts which can be employed for methane activation and conversions.},
doi = {10.1021/acs.jpclett.2c00885},
journal = {Journal of Physical Chemistry Letters},
number = 24,
volume = 13,
place = {United States},
year = {Tue Jun 14 00:00:00 EDT 2022},
month = {Tue Jun 14 00:00:00 EDT 2022}
}
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