Interfacial electron transfer in FeII(CN)6 4--sensitized TiO2 nanoparticles: A study of direct charge injection by electroabsorption spectroscopy

Electroabsorption (Stark) spectroscopy has been used to study the dye sensitized interfacial electron transfer in an FeII(CN)6 4- donor complex bound to a TiO2 nanoparticle. The average charge-transfer distance determined from the Stark spectra is 5.3 Å. This value is similar to the estimated distan...

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Autores principales: Khoudiakov, M., Parise, A.R., Brunschwig, B.S.
Formato: JOUR
Materias:
Absorption spectroscopy
Cyanides
Electron transitions
Nanostructured materials
Titanium dioxide
Stark spectroscopy
Iron compounds
dye
ferrocyanide
iron
ligand
metal complex
nanoparticle
nitrogen
titanium
titanium dioxide
absorption spectrophotometry
article
electron transport
Acceso en línea:http://hdl.handle.net/20.500.12110/paper_00027863_v125_n15_p4637_Khoudiakov
Aporte de:
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
id todo:paper_00027863_v125_n15_p4637_Khoudiakov
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spelling todo:paper_00027863_v125_n15_p4637_Khoudiakov2023-10-03T13:53:33Z Interfacial electron transfer in FeII(CN)6 4--sensitized TiO2 nanoparticles: A study of direct charge injection by electroabsorption spectroscopy Khoudiakov, M. Parise, A.R. Brunschwig, B.S. Absorption spectroscopy Cyanides Electron transitions Nanostructured materials Titanium dioxide Stark spectroscopy Iron compounds dye ferrocyanide iron ligand metal complex nanoparticle nitrogen titanium titanium dioxide absorption spectrophotometry article electron transport Electroabsorption (Stark) spectroscopy has been used to study the dye sensitized interfacial electron transfer in an FeII(CN)6 4- donor complex bound to a TiO2 nanoparticle. The average charge-transfer distance determined from the Stark spectra is 5.3 Å. This value is similar to the estimated distance between the FeII center of the complex and the TiIV surface site coordinated to the nitrogen end of a bridging CN ligand in (CN)5FeII-CN-TiIV(particle). This finding suggests that the electron injection is to either an individual titanium surface site or a small number of Ti centers localized around the point of ferrocyanide coordination to the particle and not into a conduction band orbital delocalized over the nanoparticle. The polarizability change, Tr(Δα), between the ground and the excited states of the FeII(CN)6 4--TiO2(particle) system is ∼3 time larger than normally observed in mixed-valence dinuclear metal complexes. It is proposed that the large polarizability of the excited state increases the dipole-moment changes measured by Stark spectroscopy. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_00027863_v125_n15_p4637_Khoudiakov
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic Absorption spectroscopy
Cyanides
Electron transitions
Nanostructured materials
Titanium dioxide
Stark spectroscopy
Iron compounds
dye
ferrocyanide
iron
ligand
metal complex
nanoparticle
nitrogen
titanium
titanium dioxide
absorption spectrophotometry
article
electron transport
spellingShingle Absorption spectroscopy
Cyanides
Electron transitions
Nanostructured materials
Titanium dioxide
Stark spectroscopy
Iron compounds
dye
ferrocyanide
iron
ligand
metal complex
nanoparticle
nitrogen
titanium
titanium dioxide
absorption spectrophotometry
article
electron transport
Khoudiakov, M.
Parise, A.R.
Brunschwig, B.S.
Interfacial electron transfer in FeII(CN)6 4--sensitized TiO2 nanoparticles: A study of direct charge injection by electroabsorption spectroscopy
topic_facet Absorption spectroscopy
Cyanides
Electron transitions
Nanostructured materials
Titanium dioxide
Stark spectroscopy
Iron compounds
dye
ferrocyanide
iron
ligand
metal complex
nanoparticle
nitrogen
titanium
titanium dioxide
absorption spectrophotometry
article
electron transport
description Electroabsorption (Stark) spectroscopy has been used to study the dye sensitized interfacial electron transfer in an FeII(CN)6 4- donor complex bound to a TiO2 nanoparticle. The average charge-transfer distance determined from the Stark spectra is 5.3 Å. This value is similar to the estimated distance between the FeII center of the complex and the TiIV surface site coordinated to the nitrogen end of a bridging CN ligand in (CN)5FeII-CN-TiIV(particle). This finding suggests that the electron injection is to either an individual titanium surface site or a small number of Ti centers localized around the point of ferrocyanide coordination to the particle and not into a conduction band orbital delocalized over the nanoparticle. The polarizability change, Tr(Δα), between the ground and the excited states of the FeII(CN)6 4--TiO2(particle) system is ∼3 time larger than normally observed in mixed-valence dinuclear metal complexes. It is proposed that the large polarizability of the excited state increases the dipole-moment changes measured by Stark spectroscopy.
format JOUR
author Khoudiakov, M.
Parise, A.R.
Brunschwig, B.S.
author_facet Khoudiakov, M.
Parise, A.R.
Brunschwig, B.S.
author_sort Khoudiakov, M.
title Interfacial electron transfer in FeII(CN)6 4--sensitized TiO2 nanoparticles: A study of direct charge injection by electroabsorption spectroscopy
title_short Interfacial electron transfer in FeII(CN)6 4--sensitized TiO2 nanoparticles: A study of direct charge injection by electroabsorption spectroscopy
title_full Interfacial electron transfer in FeII(CN)6 4--sensitized TiO2 nanoparticles: A study of direct charge injection by electroabsorption spectroscopy
title_fullStr Interfacial electron transfer in FeII(CN)6 4--sensitized TiO2 nanoparticles: A study of direct charge injection by electroabsorption spectroscopy
title_full_unstemmed Interfacial electron transfer in FeII(CN)6 4--sensitized TiO2 nanoparticles: A study of direct charge injection by electroabsorption spectroscopy
title_sort interfacial electron transfer in feii(cn)6 4--sensitized tio2 nanoparticles: a study of direct charge injection by electroabsorption spectroscopy
url http://hdl.handle.net/20.500.12110/paper_00027863_v125_n15_p4637_Khoudiakov
work_keys_str_mv AT khoudiakovm interfacialelectrontransferinfeiicn64sensitizedtio2nanoparticlesastudyofdirectchargeinjectionbyelectroabsorptionspectroscopy
AT parisear interfacialelectrontransferinfeiicn64sensitizedtio2nanoparticlesastudyofdirectchargeinjectionbyelectroabsorptionspectroscopy
AT brunschwigbs interfacialelectrontransferinfeiicn64sensitizedtio2nanoparticlesastudyofdirectchargeinjectionbyelectroabsorptionspectroscopy
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