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Shape-controlled pathways in the hydrogen production from ethanol steam reforming over ceria nanoparticles

Julia Vecchietti1, Patricia Pérez-Bailac2,3, Pablo G. Lustemberg2,4*, Esteban L. Fornero1, Laura Pascual2, Marta Bosco1, Arturo Martínez-Arias2, M. Veronica Ganduglia-Pirovano2, Adrian L. Bonivardi1,5

1 Instituto de Desarrollo Tecnológico para la Industria Química, UNL-CONICET, Güemes 3450, 3000 Santa Fe, Argentina.

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

3 PhD Programme in Applied Chemistry, Doctoral School, Universidad Autónoma de Madrid, C/Francisco Tomas y Valiente 2, 28049 Madrid, Spain

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

5 Facultad de Ingeniería Química, Universidad Nacional del Litoral, Santiago del Estero 2829, 3000 Santa Fe, Argentina

* Corresponding authors emails: lustemberg@gmail.com
DOI10.24435/materialscloud:1p-7e [version v1]

Publication date: Jul 19, 2022

How to cite this record

Julia Vecchietti, Patricia Pérez-Bailac, Pablo G. Lustemberg, Esteban L. Fornero, Laura Pascual, Marta Bosco, Arturo Martínez-Arias, M. Veronica Ganduglia-Pirovano, Adrian L. Bonivardi, Shape-controlled pathways in the hydrogen production from ethanol steam reforming over ceria nanoparticles, Materials Cloud Archive 2022.96 (2022), doi: 10.24435/materialscloud:1p-7e.

Description

The ethanol surface reaction over CeO₂ nanooctahedra (NO) and nanocubes (NC), which mainly expose (111) and (100) surfaces, respectively, was studied by means of infrared spectroscopy (TPSR-IR), mass spectrometry (TPSR-MS) and density functional theory (DFT) calculations. TPSR-MS results show that the production of H₂ is 2.4 times higher on CeO₂ -NC than on -NO, which is rationalized starting from the different types of adsorbed ethoxy species controlled by the shape of the ceria particles. Over the CeO₂(111) surface, monodentate type I and II ethoxy species with the alkyl chain perpendicular or parallel to the surface, respectively, were identified. Whereas on the CeO₂(100) surface, bidentate and monodentate type III ethoxy species on the checkerboard O-terminated and on a pyramid of the reconstructed (100) surface, respectively, are found. The more labile surface ethoxy species on each ceria nanoshape, which are the monodentate type I or III ethoxy on CeO₂ -NO and -NC, respectively, react on the surface to give acetate species that decomposes to CO₂ and CH₄, while H₂ is formed via the recombination of hydroxyl species. In addition, the more stable monodentate type II and bidentate ethoxy species on CeO₂ -NO and -NC, respectively, give an ethylenedioxy intermediate the binding of which is facet dependent. On the (111) facet, the less strongly bound ethylenedioxy desorbs as ethylene, whereas on the (100) facet, the more strongly bound intermediate also produces CO₂ and H₂ via formate species. Thus, on the (100) facet an additional pathway towards H₂ formation is found. ESR activity measurements show an enhanced H₂ production on the nanocubes.

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Files

File name Size Description
README.txt
MD5md5:dda7ddb6d10d5228ac61a19758d5fc0e
2.9 KiB Description of the data loaded in this record
molecules_gas_phase.zip
MD5md5:387ca0a7c1ffa2fd4ffc0e9b8913f631
585.7 KiB It contains ethanol and water in the gas phase
surfaces.zip
MD5md5:7334db06bcc4459171dc3e43bbfb45cd
10.5 MiB It contains the ceria surface models as described in the manuscript.
adsorbed_molecules.zip
MD5md5:eadf7c6dd9ec2b508b41953344173aa7
146.4 MiB It contains 13 folders with 10 kinds of ethoxy states, 2 ethylenedioxy and one ethylene on both surfaces of CeO2(111) and (100) and with different degree of hydroxylation.

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.

External references

Journal reference
J. Vecchietti, P. Pérez-Bailac, P. G. Lustemberg, E. L. Fornero, L. Pascual, M. Bosco, A. Martínez-Arias, M. V. Ganduglia-Pirovano, A. L. Bonivardi, ACS Cata., 12, 10482-10498 (2022)

Keywords

ceria nanostructures green hydrogen ethanol decomposition ethylenedioxy species facet-dependent activity

Version history:

2022.96 (version v1) [This version] Jul 19, 2022 DOI10.24435/materialscloud:1p-7e