Density Functional Theory Study of Metal and Metal-Oxide Nucleation and Growth on the Anatase TiO<sub>2</sub>(101) Surface

Density Functional Theory Study of Metal and Metal-Oxide Nucleation and Growth on the Anatase TiO<sub>2</sub>(101) Surface

Experimental studies have shown the possible production of hydrogen through photocatalytic water splitting using metal oxide (MO<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><...

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Autores principales: Leila Kalantari, Fabien Tran, Peter Blaha
Formato: article
Lenguaje:EN
Publicado: MDPI AG 2021
Materias:
DFT
anatase TiO<sub>2</sub>(101) surface
adsorption energy
Bader charge
Electronic computers. Computer science
QA75.5-76.95
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spelling oai:doaj.org-article:7f2eac5a04a34fc49d5f9c65fdd9ecd92021-11-25T17:17:19ZDensity Functional Theory Study of Metal and Metal-Oxide Nucleation and Growth on the Anatase TiO<sub>2</sub>(101) Surface10.3390/computation91101252079-3197https://doaj.org/article/7f2eac5a04a34fc49d5f9c65fdd9ecd92021-11-01T00:00:00Zhttps://www.mdpi.com/2079-3197/9/11/125https://doaj.org/toc/2079-3197Experimental studies have shown the possible production of hydrogen through photocatalytic water splitting using metal oxide (MO<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mi>y</mi></msub></semantics></math></inline-formula>) nanoparticles attached to an anatase TiO<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula> surface. In this work, we performed density functional theory (DFT) calculations to provide a detailed description of the stability and geometry of M<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mi>x</mi></msub></semantics></math></inline-formula>O<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mi>y</mi></msub></semantics></math></inline-formula> clusters M = Cu, Ni, Co, Fe and Mn, <i>x</i> = 1–5, and <i>y</i> = 0–5 on the anatase TiO<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula>(101) surface. It is found that unsaturated 2-fold-coordinated O-sites may serve as nucleation centers for the growth of metal clusters. The formation energy of Ni-containing clusters on the anatase surface is larger than for other M clusters. In addition, the Ni<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mi>n</mi></msub></semantics></math></inline-formula> adsorption energy increases with cluster size <i>n</i>, which makes the formation of bigger Ni clusters plausible as confirmed by transition electron microscopy images. Another particularity for Ni-containing clusters is that the adsorption energy per atom gets larger when the O-content is reduced, while for other M atoms it remains almost constant or, as for Mn, even decreases. This trend is in line with experimental results. Also provided is a discussion of the oxidation states of M<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>5</mn></msub></semantics></math></inline-formula>O<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mi>y</mi></msub></semantics></math></inline-formula> clusters based on their magnetic moments and Bader charges and their possible reduction with oxygen depletion.Leila KalantariFabien TranPeter BlahaMDPI AGarticleDFTanatase TiO<sub>2</sub>(101) surfaceadsorption energyBader chargeElectronic computers. Computer scienceQA75.5-76.95ENComputation, Vol 9, Iss 125, p 125 (2021)
institution DOAJ
collection DOAJ
language EN
topic DFT
anatase TiO<sub>2</sub>(101) surface
adsorption energy
Bader charge
Electronic computers. Computer science
QA75.5-76.95
spellingShingle DFT
anatase TiO<sub>2</sub>(101) surface
adsorption energy
Bader charge
Electronic computers. Computer science
QA75.5-76.95
Leila Kalantari
Fabien Tran
Peter Blaha
Density Functional Theory Study of Metal and Metal-Oxide Nucleation and Growth on the Anatase TiO<sub>2</sub>(101) Surface
description Experimental studies have shown the possible production of hydrogen through photocatalytic water splitting using metal oxide (MO<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mi>y</mi></msub></semantics></math></inline-formula>) nanoparticles attached to an anatase TiO<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula> surface. In this work, we performed density functional theory (DFT) calculations to provide a detailed description of the stability and geometry of M<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mi>x</mi></msub></semantics></math></inline-formula>O<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mi>y</mi></msub></semantics></math></inline-formula> clusters M = Cu, Ni, Co, Fe and Mn, <i>x</i> = 1–5, and <i>y</i> = 0–5 on the anatase TiO<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula>(101) surface. It is found that unsaturated 2-fold-coordinated O-sites may serve as nucleation centers for the growth of metal clusters. The formation energy of Ni-containing clusters on the anatase surface is larger than for other M clusters. In addition, the Ni<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mi>n</mi></msub></semantics></math></inline-formula> adsorption energy increases with cluster size <i>n</i>, which makes the formation of bigger Ni clusters plausible as confirmed by transition electron microscopy images. Another particularity for Ni-containing clusters is that the adsorption energy per atom gets larger when the O-content is reduced, while for other M atoms it remains almost constant or, as for Mn, even decreases. This trend is in line with experimental results. Also provided is a discussion of the oxidation states of M<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>5</mn></msub></semantics></math></inline-formula>O<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mi>y</mi></msub></semantics></math></inline-formula> clusters based on their magnetic moments and Bader charges and their possible reduction with oxygen depletion.
format article
author Leila Kalantari
Fabien Tran
Peter Blaha
author_facet Leila Kalantari
Fabien Tran
Peter Blaha
author_sort Leila Kalantari
title Density Functional Theory Study of Metal and Metal-Oxide Nucleation and Growth on the Anatase TiO<sub>2</sub>(101) Surface
title_short Density Functional Theory Study of Metal and Metal-Oxide Nucleation and Growth on the Anatase TiO<sub>2</sub>(101) Surface
title_full Density Functional Theory Study of Metal and Metal-Oxide Nucleation and Growth on the Anatase TiO<sub>2</sub>(101) Surface
title_fullStr Density Functional Theory Study of Metal and Metal-Oxide Nucleation and Growth on the Anatase TiO<sub>2</sub>(101) Surface
title_full_unstemmed Density Functional Theory Study of Metal and Metal-Oxide Nucleation and Growth on the Anatase TiO<sub>2</sub>(101) Surface
title_sort density functional theory study of metal and metal-oxide nucleation and growth on the anatase tio<sub>2</sub>(101) surface
publisher MDPI AG
publishDate 2021
url https://doaj.org/article/7f2eac5a04a34fc49d5f9c65fdd9ecd9
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AT fabientran densityfunctionaltheorystudyofmetalandmetaloxidenucleationandgrowthontheanatasetiosub2sub101surface
AT peterblaha densityfunctionaltheorystudyofmetalandmetaloxidenucleationandgrowthontheanatasetiosub2sub101surface
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