Pablo G. Lustemberg^1*, Zhongtian Mao², Agustín Salcedo^3,4, Beatriz Irigoyen^3,4, M. Verónica Ganduglia-Pirovano¹, Charles T. Campbell²

1 Instituto de Catálisis y Petroleoquímica (ICP-CSIC), C/Marie Curie 2, 28049 Madrid, Spain

2 Department of Chemistry, University of Washington, Seattle, Washington 98195-1700, USA

3 Universidad de Buenos Aires (UBA), Facultad de Ingeniería, Departamento de Ingeniería Química, Ciudad Universitaria, C1428EGA Buenos Aires, Argentina

4 Instituto de Tecnologías de Hidrógeno y Energías Sostenibles (ITHES, CONICET-UBA), Ciudad Universitaria, C1428EGA Buenos Aires, Argentina

* Corresponding authors emails: p.lustemberg@csic.es

DOI10.24435/materialscloud:ks-qb [version v1]

Publication date: May 21, 2021

How to cite this record

Pablo G. Lustemberg, Zhongtian Mao, Agustín Salcedo, Beatriz Irigoyen, M. Verónica Ganduglia-Pirovano, Charles T. Campbell, The nature of the active sites on Ni/CeO2 catalysts for methane conversions, Materials Cloud Archive 2021.78 (2021), https://doi.org/10.24435/materialscloud:ks-qb

Description

Effective catalysts for the direct conversion of methane to methanol and for methane’s dry reforming to syngas are Holy Grails of catalysis research toward clean energy technologies. It has recently been discovered that Ni at low loadings on CeO2 is very reactive towards reactants CH4, H2O and CO2 and active for both of these reactions. Revealing the nature of the active sites in such systems is paramount to a rational design of improved catalysts. Here, using a combination of experimental measurements and density functional theory calculations, we show that the most active sites are cationic Ni atoms in clusters at step edges on the CeO2 surface, using the activation of CH4 as an example . We show that the size and morphology of the supported nanoparticles together with strong Ni−support bonding and charge transfer at the step edge are key to the high catalytic activity towards these methane conversions. We anticipate that this knowledge will inspire the development of more efficient catalysts for these reactions.

Materials Cloud sections using this data

Files

File name	Size	Description
README.txt MD5md5:9d1a4f810cd2d290d324308ea7fec0b0	1.9 KiB	Readme file
Ni1.CeO2.zip MD5md5:55d0d53298b874d3b00e742b9481a699	182.4 MiB	DFT calculations corresponding to the methane adsorbed (CH4), dissociated (CH3+H) and transition (TS) states on Ni1.CeO2 catalyst.
Ni5+1.step.CeO2.zip MD5md5:d8946ab081bf8bcdde3b16f63fc4a725	14.7 MiB	DFT calculations corresponding to the methane adsorbed (CH4), dissociated (CH3+H) and transition (TS) states on Ni5+1.step.CeO2 catalyst for the Cooperative and Non-Cooperative pathways defined in the manuscript.
Ni4.2D.CeO2.zip MD5md5:8e003c019f9f09cd7ab34f7a7b8ea730	168.7 MiB	DFT calculations corresponding to the methane adsorbed (CH4), dissociated (CH3+H) and transition (TS) states on Ni4.2D.CeO2 catalyst for the Cooperative and Non-Cooperative pathways defined in the manuscript.
Ni13.CeO2.zip MD5md5:98b43e64c2357aa869e49f7b6b880ef5	303.2 MiB	DFT calculations corresponding to the methane adsorbed (CH4), dissociated (CH3+H) and transition (TS) states on the interface or terrace of the Ni13.CeO2 catalyst.
cat.zip MD5md5:72f96b4c0f2147ae07b8d57a7d174555	934.1 MiB	DFT calculations corresponding to the 4 models of Ni nanoclusters on CeO2(111): Ni1, Ni4.2D, Ni13 and Ni5+1.step and the DFT calculations corresponding to the 4 models of Ni nanoclusters in gas phase: Ni1.gas, Ni4.2D.gas, Ni13.gas and Ni5+1.step.gas

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External references

Keywords

DFT+U+V Ni clusters on CeO2 CH4 dissociation