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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/CeO₂ catalysts

Pablo G. Lustemberg1,2*, Sanjaya D. Senanayake3, Jose A. Rodriguez3, M. Verónica Ganduglia-Pirovano1*

1 Institute of Catalysis and Petrochemistry, ICP, Spanish National Research Council, CSIC, 28049 Madrid, Spain

2 Institute of Physics Rosario, IFIR, National Scientific and Technical Research Council, CONICET, S2000EKF Rosario, Santa Fe, Argentina

3 Chemistry Division, Brookhaven National Laboratory, Upton, New York 11973, United States

* Corresponding authors emails: p.lustemberg@csic.es, vgp@icp.csic.es
DOI10.24435/materialscloud:8y-7m [version v1]

Publication date: Jun 10, 2022

How to cite this record

Pablo G. Lustemberg, Sanjaya D. Senanayake, Jose A. Rodriguez, M. Verónica Ganduglia-Pirovano, 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/CeO₂ catalysts, Materials Cloud Archive 2022.75 (2022), doi: 10.24435/materialscloud:8y-7m.

Description

The efficient activation of methane and 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 on both Ni and Cu sites. The MTM reaction pathway for the example of the Ni₃Cu₁/CeO₂ model catalyst predict 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.

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Files

File name Size Description
CH4gas_H2Ogas.zip
MD5md5:501c7dea6db8deeef6162062c9455db9
49.6 KiB DFT calculations of CH4 and H2O in gas phase
Models.zip
MD5md5:5a629881cfc183e3e89f69d070d4160e
13.3 MiB Includes the DFT calculations of the following surfaces models: Cu(111), Ni(111), Cu4.CeO2, Ni4.CeO2, Ni1Cu3.CeO2, Ni2Cu2.CeO2 and Ni3Cu1.CeO2
Methane_Activation.zip
MD5md5:9eecf45c554a05ea75a663e7ec1981a1
167.5 MiB Includes the DFT calculations of Methane adsorption and activation on: Cu(111), Ni(111), Cu4.CeO2, Ni4.CeO2, Ni1Cu3.CeO2, Ni2Cu2.CeO2 and Ni3Cu1.CeO2. Also, the intermediate states of the complete decomposition of CH4 are found.
Hydrogen_Adsorption.zip
MD5md5:38367b56da2d1683be45c1dbb6faf4c0
3.4 MiB Includes the DFT calculations of Hydrogen atom adsorbed on: Cu4.CeO2, Ni4.CeO2, Ni1Cu3.CeO2, Ni2Cu2.CeO2 and Ni3Cu1.CeO2
Water_Activation.zip
MD5md5:3adf06bcc3fd96895eb1277f8423d0f8
56.5 MiB Includes the DFT calculations of Water adsorption and activation on: Cu(111), Ni(111), Cu4.CeO2, Ni4.CeO2, Ni1Cu3.CeO2, Ni2Cu2.CeO2 and Ni3Cu1.CeO2
Methanol_Formation.zip
MD5md5:83af6eb1ea86cbf00b5564710d0a7e6d
91.1 MiB It contains all the relevant states for the formation of methanol from CH4 and O adsorbed on the Ni4.CeO2 and Ni3Cu1.CeO2 surfaces (see Figure 4 of the manuscript).
README.txt
MD5md5:b2d37dc24276d9e3c49367d3dde10f06
2.4 KiB Readme file with the relevant data description

License

Files and data are licensed under the terms of the following license: Creative Commons Attribution 4.0 International.
Metadata, except for email addresses, are licensed under the Creative Commons Attribution Share-Alike 4.0 International license.

Keywords

bimetallic ceria methane activation water activation

Version history:

2022.75 (version v1) [This version] Jun 10, 2022 DOI10.24435/materialscloud:8y-7m