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H2 Dissociation and Oxygen Vacancy Formation on Ce2O3 Surfaces

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Abstract

H2 dissociation on ceria (CeO2) has attracted much attention in the last years because of its potential application in catalysis for hydrogenation reactions, as well as for the stabilization of hydride bulk and surface species. The ability of ceria to split hydrogen is strongly dependent on the surface morphology. However, to the best of our knowledge, the reactivity of the cerium sesquioxide Ce2O3 A-type (hexagonal structure with space group \(P\bar{3}m1\)) has not been previously addressed. In the present study, we investigate (i) the formation of oxygen vacancies in A-Ce2O3 bulk and (ii) the effect of the surface topology in the H2 dissociation and in the oxygen vacancy formation for the four most stable surfaces of A-Ce2O3: (0001), (01− 11), (11− 20) and (11− 21). Our results indicate a significant decrease of the energetic barrier for the hydrogen dissociation compared to stoichiometric CeO2, with an activation energy of ~ 0.1 eV. Interestingly, Ce2O3 surfaces lead to a heterolytic product with hydride species more stable than the homolytic product, which is the opposite behavior found in CeO2. These results suggest a better performance of Ce2O3 than CeO2 for H2 dissociation and provide insight in the nature of hydride-Ce2O3 interfaces that could be important intermediates in the formation of CeHx phases from cerium oxide.

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Acknowledgements

Authors acknowledge Scienomics for the MAPS program used in the construction of the slab models for a courtesy license. Dr. B. Diawara is acknowledged for the Modelview program. This work was performed using HPC resources from GENCI-CINES/IDRIS (Grant Nos. 2018-x2018082131 and 2017-x2017082131), and the PER-SU iDROGEN project.

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  1. Laboratoire de Chimie Théorique, LCT, Sorbonne Université, CNRS, 75005, Paris, France

    O. Matz & M. Calatayud

  2. Laboratoire de Chimie Théorique, Sorbonne Université, 4, Place Jussieu Case 137, 75252, Paris Cedex 5, France

    M. Calatayud

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11244_2019_1183_MOESM1_ESM.docx

Results of the choice of the cutoff for the bulk and thickness convergence tests for all the slab model. The structures (POSCAR format) of bare slabs, TS and (H+,H−) minima were also given. The DOS and PDOS of oxygen vacancies as well as the different steps involved in H2 dissociation were provided for all the surfaces. Supplementary material 1 (DOCX 26501 kb)

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Matz, O., Calatayud, M. H2 Dissociation and Oxygen Vacancy Formation on Ce2O3 Surfaces. Top Catal 62, 956–967 (2019). https://doi.org/10.1007/s11244-019-01183-0

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