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How mobile are dye adsorbates and acetonitrile molecules on the surface of TiO(2) nanoparticles? A quasi-elastic neutron scattering study

Motions of molecules adsorbed to surfaces may control the rate of charge transport within monolayers in systems such as dye sensitized solar cells. We used quasi-elastic neutron scattering (QENS) to evaluate the possible dynamics of two small dye moieties, isonicotinic acid (INA) and bis-isonicotini...

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Autores principales: Vaissier, Valerie, Sakai, Victoria Garcia, Li, Xiaoe, Cabral, João T., Nelson, Jenny, Barnes, Piers R. F.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group 2016
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5171786/
https://www.ncbi.nlm.nih.gov/pubmed/27991538
http://dx.doi.org/10.1038/srep39253
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author Vaissier, Valerie
Sakai, Victoria Garcia
Li, Xiaoe
Cabral, João T.
Nelson, Jenny
Barnes, Piers R. F.
author_facet Vaissier, Valerie
Sakai, Victoria Garcia
Li, Xiaoe
Cabral, João T.
Nelson, Jenny
Barnes, Piers R. F.
author_sort Vaissier, Valerie
collection PubMed
description Motions of molecules adsorbed to surfaces may control the rate of charge transport within monolayers in systems such as dye sensitized solar cells. We used quasi-elastic neutron scattering (QENS) to evaluate the possible dynamics of two small dye moieties, isonicotinic acid (INA) and bis-isonicotinic acid (BINA), attached to TiO(2) nanoparticles via carboxylate groups. The scattering data indicate that moieties are immobile and do not rotate around the anchoring groups on timescales between around 10 ps and a few ns (corresponding to the instrumental range). This gives an upper limit for the rate at which conformational fluctuations can assist charge transport between anchored molecules. Our observations suggest that if the conformation of larger dye molecules varies with time, it does so on longer timescales and/or in parts of the molecule which are not directly connected to the anchoring group. The QENS measurements also indicate that several layers of acetonitrile solvent molecules are immobilized at the interface with the TiO(2) on the measurement time scale, in reasonable agreement with recent classical molecular dynamics results.
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spelling pubmed-51717862016-12-28 How mobile are dye adsorbates and acetonitrile molecules on the surface of TiO(2) nanoparticles? A quasi-elastic neutron scattering study Vaissier, Valerie Sakai, Victoria Garcia Li, Xiaoe Cabral, João T. Nelson, Jenny Barnes, Piers R. F. Sci Rep Article Motions of molecules adsorbed to surfaces may control the rate of charge transport within monolayers in systems such as dye sensitized solar cells. We used quasi-elastic neutron scattering (QENS) to evaluate the possible dynamics of two small dye moieties, isonicotinic acid (INA) and bis-isonicotinic acid (BINA), attached to TiO(2) nanoparticles via carboxylate groups. The scattering data indicate that moieties are immobile and do not rotate around the anchoring groups on timescales between around 10 ps and a few ns (corresponding to the instrumental range). This gives an upper limit for the rate at which conformational fluctuations can assist charge transport between anchored molecules. Our observations suggest that if the conformation of larger dye molecules varies with time, it does so on longer timescales and/or in parts of the molecule which are not directly connected to the anchoring group. The QENS measurements also indicate that several layers of acetonitrile solvent molecules are immobilized at the interface with the TiO(2) on the measurement time scale, in reasonable agreement with recent classical molecular dynamics results. Nature Publishing Group 2016-12-19 /pmc/articles/PMC5171786/ /pubmed/27991538 http://dx.doi.org/10.1038/srep39253 Text en Copyright © 2016, The Author(s) http://creativecommons.org/licenses/by/4.0/ This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/
spellingShingle Article
Vaissier, Valerie
Sakai, Victoria Garcia
Li, Xiaoe
Cabral, João T.
Nelson, Jenny
Barnes, Piers R. F.
How mobile are dye adsorbates and acetonitrile molecules on the surface of TiO(2) nanoparticles? A quasi-elastic neutron scattering study
title How mobile are dye adsorbates and acetonitrile molecules on the surface of TiO(2) nanoparticles? A quasi-elastic neutron scattering study
title_full How mobile are dye adsorbates and acetonitrile molecules on the surface of TiO(2) nanoparticles? A quasi-elastic neutron scattering study
title_fullStr How mobile are dye adsorbates and acetonitrile molecules on the surface of TiO(2) nanoparticles? A quasi-elastic neutron scattering study
title_full_unstemmed How mobile are dye adsorbates and acetonitrile molecules on the surface of TiO(2) nanoparticles? A quasi-elastic neutron scattering study
title_short How mobile are dye adsorbates and acetonitrile molecules on the surface of TiO(2) nanoparticles? A quasi-elastic neutron scattering study
title_sort how mobile are dye adsorbates and acetonitrile molecules on the surface of tio(2) nanoparticles? a quasi-elastic neutron scattering study
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5171786/
https://www.ncbi.nlm.nih.gov/pubmed/27991538
http://dx.doi.org/10.1038/srep39253
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