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Water Adsorption on MO(2) (M = Ti, Ru, and Ir) Surfaces. Importance of Octahedral Distortion and Cooperative Effects

[Image: see text] Understanding metal oxide MO(2) (M = Ti, Ru, and Ir)–water interfaces is essential to assess the catalytic behavior of these materials. The present study analyzes the H(2)O–MO(2) interactions at the most abundant (110) and (011) surfaces, at two different water coverages: isolated...

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Autores principales: González, Danilo, Heras-Domingo, Javier, Pantaleone, Stefano, Rimola, Albert, Rodríguez-Santiago, Luis, Solans-Monfort, Xavier, Sodupe, Mariona
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2019
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6649029/
https://www.ncbi.nlm.nih.gov/pubmed/31459524
http://dx.doi.org/10.1021/acsomega.8b03350
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author González, Danilo
Heras-Domingo, Javier
Pantaleone, Stefano
Rimola, Albert
Rodríguez-Santiago, Luis
Solans-Monfort, Xavier
Sodupe, Mariona
author_facet González, Danilo
Heras-Domingo, Javier
Pantaleone, Stefano
Rimola, Albert
Rodríguez-Santiago, Luis
Solans-Monfort, Xavier
Sodupe, Mariona
author_sort González, Danilo
collection PubMed
description [Image: see text] Understanding metal oxide MO(2) (M = Ti, Ru, and Ir)–water interfaces is essential to assess the catalytic behavior of these materials. The present study analyzes the H(2)O–MO(2) interactions at the most abundant (110) and (011) surfaces, at two different water coverages: isolated water molecules and full monolayer, by means of Perdew–Burke–Ernzerhof-D2 static calculations and ab initio molecular dynamics (AIMD) simulations. Results indicate that adsorption preferably occurs in its molecular form on (110)-TiO(2) and in its dissociative form on (110)-RuO(2) and (110)-IrO(2). The opposite trend is observed at the (011) facet. This different behavior is related to the kind of octahedral distortion observed in the bulk of these materials (tetragonal elongation for TiO(2) and tetragonal compression for RuO(2) and IrO(2)) and to the different nature of the vacant sites created, axial on (110) and equatorial on (011). For the monolayer, additional effects such as cooperative H-bond interactions and cooperative adsorption come into play in determining the degree of deprotonation. For TiO(2), AIMD indicates that the water monolayer is fully undissociated at both (110) and (011) surfaces, whereas for RuO(2), water monolayer exhibits a 50% dissociation, the formation of H(3)O(2)(–) motifs being essential. Finally, on (110)-IrO(2), the main monolayer configuration is the fully dissociated one, whereas on (011)-IrO(2), it exhibits a degree of dissociation that ranges between 50 and 75%. Overall, the present study shows that the degree of water dissociation results from a delicate balance between the H(2)O–MO(2) intrinsic interaction and cooperative hydrogen bonding and adsorption effects.
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spelling pubmed-66490292019-08-27 Water Adsorption on MO(2) (M = Ti, Ru, and Ir) Surfaces. Importance of Octahedral Distortion and Cooperative Effects González, Danilo Heras-Domingo, Javier Pantaleone, Stefano Rimola, Albert Rodríguez-Santiago, Luis Solans-Monfort, Xavier Sodupe, Mariona ACS Omega [Image: see text] Understanding metal oxide MO(2) (M = Ti, Ru, and Ir)–water interfaces is essential to assess the catalytic behavior of these materials. The present study analyzes the H(2)O–MO(2) interactions at the most abundant (110) and (011) surfaces, at two different water coverages: isolated water molecules and full monolayer, by means of Perdew–Burke–Ernzerhof-D2 static calculations and ab initio molecular dynamics (AIMD) simulations. Results indicate that adsorption preferably occurs in its molecular form on (110)-TiO(2) and in its dissociative form on (110)-RuO(2) and (110)-IrO(2). The opposite trend is observed at the (011) facet. This different behavior is related to the kind of octahedral distortion observed in the bulk of these materials (tetragonal elongation for TiO(2) and tetragonal compression for RuO(2) and IrO(2)) and to the different nature of the vacant sites created, axial on (110) and equatorial on (011). For the monolayer, additional effects such as cooperative H-bond interactions and cooperative adsorption come into play in determining the degree of deprotonation. For TiO(2), AIMD indicates that the water monolayer is fully undissociated at both (110) and (011) surfaces, whereas for RuO(2), water monolayer exhibits a 50% dissociation, the formation of H(3)O(2)(–) motifs being essential. Finally, on (110)-IrO(2), the main monolayer configuration is the fully dissociated one, whereas on (011)-IrO(2), it exhibits a degree of dissociation that ranges between 50 and 75%. Overall, the present study shows that the degree of water dissociation results from a delicate balance between the H(2)O–MO(2) intrinsic interaction and cooperative hydrogen bonding and adsorption effects. American Chemical Society 2019-02-11 /pmc/articles/PMC6649029/ /pubmed/31459524 http://dx.doi.org/10.1021/acsomega.8b03350 Text en Copyright © 2019 American Chemical Society This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes.
spellingShingle González, Danilo
Heras-Domingo, Javier
Pantaleone, Stefano
Rimola, Albert
Rodríguez-Santiago, Luis
Solans-Monfort, Xavier
Sodupe, Mariona
Water Adsorption on MO(2) (M = Ti, Ru, and Ir) Surfaces. Importance of Octahedral Distortion and Cooperative Effects
title Water Adsorption on MO(2) (M = Ti, Ru, and Ir) Surfaces. Importance of Octahedral Distortion and Cooperative Effects
title_full Water Adsorption on MO(2) (M = Ti, Ru, and Ir) Surfaces. Importance of Octahedral Distortion and Cooperative Effects
title_fullStr Water Adsorption on MO(2) (M = Ti, Ru, and Ir) Surfaces. Importance of Octahedral Distortion and Cooperative Effects
title_full_unstemmed Water Adsorption on MO(2) (M = Ti, Ru, and Ir) Surfaces. Importance of Octahedral Distortion and Cooperative Effects
title_short Water Adsorption on MO(2) (M = Ti, Ru, and Ir) Surfaces. Importance of Octahedral Distortion and Cooperative Effects
title_sort water adsorption on mo(2) (m = ti, ru, and ir) surfaces. importance of octahedral distortion and cooperative effects
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6649029/
https://www.ncbi.nlm.nih.gov/pubmed/31459524
http://dx.doi.org/10.1021/acsomega.8b03350
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