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CO Adsorbate Promotes Polaron Photoactivity on the Reduced Rutile TiO(2)(110) Surface

[Image: see text] Polarons play a major role in determining the chemical properties of transition-metal oxides. Recent experiments show that adsorbates can attract inner polarons to surface sites. These findings require an atomistic understanding of the adsorbate influence on polaron dynamics and li...

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Autores principales: Cheng, Cheng, Zhu, Yonghao, Fang, Wei-Hai, Long, Run, Prezhdo, Oleg V.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2021
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8790733/
https://www.ncbi.nlm.nih.gov/pubmed/35098240
http://dx.doi.org/10.1021/jacsau.1c00508
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author Cheng, Cheng
Zhu, Yonghao
Fang, Wei-Hai
Long, Run
Prezhdo, Oleg V.
author_facet Cheng, Cheng
Zhu, Yonghao
Fang, Wei-Hai
Long, Run
Prezhdo, Oleg V.
author_sort Cheng, Cheng
collection PubMed
description [Image: see text] Polarons play a major role in determining the chemical properties of transition-metal oxides. Recent experiments show that adsorbates can attract inner polarons to surface sites. These findings require an atomistic understanding of the adsorbate influence on polaron dynamics and lifetime. We consider reduced rutile TiO(2)(110) with an oxygen vacancy as a prototypical surface and a CO molecule as a classic probe and perform ab initio adiabatic molecular dynamics, time-domain density functional theory, and nonadiabatic molecular dynamics simulations. The simulations show that subsurface polarons have little influence on CO adsorption and CO can desorb easily. On the contrary, surface polarons strongly enhance CO adsorption. At the same time, the adsorbed CO attracts polarons to the surface, allowing them to participate in catalytic processes with CO. The CO interaction with polarons changes their orbital origin, suppresses polaron hopping, and stabilizes them at surface sites. Partial delocalization of polarons onto CO decouples them from free holes, decreasing the nonadiabatic coupling and shortening the quantum coherence time, thereby reducing charge recombination. The calculations demonstrate that CO prefers to adsorb at the next-nearest-neighbor five-coordinated Ti(3+) surface electron polaron sites. The reported results provide a fundamental understanding of the influence of electron polarons on the initial stage of reactant adsorption and the effect of the adsorbate–polaron interaction on the polaron dynamics and lifetime. The study demonstrates how charge and polaron properties can be controlled by adsorbed species, allowing one to design high-performance transition-metal oxide catalysts.
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spelling pubmed-87907332022-01-27 CO Adsorbate Promotes Polaron Photoactivity on the Reduced Rutile TiO(2)(110) Surface Cheng, Cheng Zhu, Yonghao Fang, Wei-Hai Long, Run Prezhdo, Oleg V. JACS Au [Image: see text] Polarons play a major role in determining the chemical properties of transition-metal oxides. Recent experiments show that adsorbates can attract inner polarons to surface sites. These findings require an atomistic understanding of the adsorbate influence on polaron dynamics and lifetime. We consider reduced rutile TiO(2)(110) with an oxygen vacancy as a prototypical surface and a CO molecule as a classic probe and perform ab initio adiabatic molecular dynamics, time-domain density functional theory, and nonadiabatic molecular dynamics simulations. The simulations show that subsurface polarons have little influence on CO adsorption and CO can desorb easily. On the contrary, surface polarons strongly enhance CO adsorption. At the same time, the adsorbed CO attracts polarons to the surface, allowing them to participate in catalytic processes with CO. The CO interaction with polarons changes their orbital origin, suppresses polaron hopping, and stabilizes them at surface sites. Partial delocalization of polarons onto CO decouples them from free holes, decreasing the nonadiabatic coupling and shortening the quantum coherence time, thereby reducing charge recombination. The calculations demonstrate that CO prefers to adsorb at the next-nearest-neighbor five-coordinated Ti(3+) surface electron polaron sites. The reported results provide a fundamental understanding of the influence of electron polarons on the initial stage of reactant adsorption and the effect of the adsorbate–polaron interaction on the polaron dynamics and lifetime. The study demonstrates how charge and polaron properties can be controlled by adsorbed species, allowing one to design high-performance transition-metal oxide catalysts. American Chemical Society 2021-12-30 /pmc/articles/PMC8790733/ /pubmed/35098240 http://dx.doi.org/10.1021/jacsau.1c00508 Text en © 2021 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by-nc-nd/4.0/Permits non-commercial access and re-use, provided that author attribution and integrity are maintained; but does not permit creation of adaptations or other derivative works (https://creativecommons.org/licenses/by-nc-nd/4.0/).
spellingShingle Cheng, Cheng
Zhu, Yonghao
Fang, Wei-Hai
Long, Run
Prezhdo, Oleg V.
CO Adsorbate Promotes Polaron Photoactivity on the Reduced Rutile TiO(2)(110) Surface
title CO Adsorbate Promotes Polaron Photoactivity on the Reduced Rutile TiO(2)(110) Surface
title_full CO Adsorbate Promotes Polaron Photoactivity on the Reduced Rutile TiO(2)(110) Surface
title_fullStr CO Adsorbate Promotes Polaron Photoactivity on the Reduced Rutile TiO(2)(110) Surface
title_full_unstemmed CO Adsorbate Promotes Polaron Photoactivity on the Reduced Rutile TiO(2)(110) Surface
title_short CO Adsorbate Promotes Polaron Photoactivity on the Reduced Rutile TiO(2)(110) Surface
title_sort co adsorbate promotes polaron photoactivity on the reduced rutile tio(2)(110) surface
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8790733/
https://www.ncbi.nlm.nih.gov/pubmed/35098240
http://dx.doi.org/10.1021/jacsau.1c00508
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