Photophysics of color centers in visible-light-active rutile titania. Evidence of the photoformation and trapping of charge carriers from advanced diffuse reflectance spectroscopy and mass spectrometry

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Abstract

We herein report on the photophysics of color centers in visible-light-active (VLA) rutile titania ceramics and titania powder resulting from the photoformation and separation of charge carriers explored by a diffuse reflectance (DR) spectroscopic and kinetic study using a cryostat-type accessory for a Cary 5000 spectrophotometer after exposure of the titanias to UV radiation and Vis-light illumination. The action spectrum of the photoformation of Ti3+ at 90 K accorded fully with the absorption spectrum of intrinsic defects in the as-synthesized TiO2. The photoinduced absorption spectra consisted of a set of individual absorption bands attributable to several different Ti3+ centers. Analysis of the dependencies of the photoformation of separate centers on the wavelength of illumination and light exposure provided extraction of specific Ti3+ centers putatively attributed to centers with excess negative charge {2Ti3+ + Vo 2+} ⟵→ {Tiδ+ + Vo 2+} with 3 > δ > 2 formed at significantly high concentration upon maximal exposure to Vis-light illumination. Thermoprogrammed annealing (TPA) spectra of Ti3+ color centers photoinduced in VLA TiO2 displayed temperature dependencies of the rate of detrapping of the photoinduced holes observed optically through annihilation of the Ti3+ centers. The TPA spectra in the range 90–500 K consisted of a set of first-order peaks corresponding to the traps, whose depths ranged from ∼0.2 eV (peak at 130 K in powder specimen) to 1.06 eV (peak at 455 K in the ceramics). The highest rate of recombination of holes released to the valence band with Ti3+ centers, an event attributable to the Tiδ+ centers, provided TPA spectra that clearly manifested the existence of shallow traps. We also report mass spectrometric evidence of the photoformation of electrons and holes in VLA TiO2 under Vis-light illumination through an examination of the photoadsorption of molecular oxygen and the photodesorption of photoadsorbed oxygen from the surface of powdered VLA titania specimens. Moreover, kinetics of the photodesorption of O2 under orange light illumination, after the photoadsorption of O2 stimulated by blue light excitation, provided experimental proof of the occurrence of an additional specific channel toward the photoactivation of VLA TiO2 via the photoexcitation of photoinduced Ti3+ color centers.

Original languageEnglish
Pages (from-to)58-69
JournalCatalysis Today
Volume340
Early online date16 Oct 2018
DOIs
Publication statusPublished - 15 Jan 2020

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Color centers
Charge carriers
Mass spectrometry
Titanium
Spectroscopy
Lighting
Absorption spectra
Annealing
Powders
titanium dioxide
Kinetics
Cryostats
Molecular oxygen
Photoexcitation
Spectrophotometers
Accessories
Valence bands
Ultraviolet radiation

Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

@article{c5de0c2aa2854738a4a2d17d118bb86f,
title = "Photophysics of color centers in visible-light-active rutile titania. Evidence of the photoformation and trapping of charge carriers from advanced diffuse reflectance spectroscopy and mass spectrometry",
abstract = "We herein report on the photophysics of color centers in visible-light-active (VLA) rutile titania ceramics and titania powder resulting from the photoformation and separation of charge carriers explored by a diffuse reflectance (DR) spectroscopic and kinetic study using a cryostat-type accessory for a Cary 5000 spectrophotometer after exposure of the titanias to UV radiation and Vis-light illumination. The action spectrum of the photoformation of Ti3+ at 90 K accorded fully with the absorption spectrum of intrinsic defects in the as-synthesized TiO2. The photoinduced absorption spectra consisted of a set of individual absorption bands attributable to several different Ti3+ centers. Analysis of the dependencies of the photoformation of separate centers on the wavelength of illumination and light exposure provided extraction of specific Ti3+ centers putatively attributed to centers with excess negative charge {2Ti3+ + Vo 2+} ⟵→ {Tiδ+ + Vo 2+} with 3 > δ > 2 formed at significantly high concentration upon maximal exposure to Vis-light illumination. Thermoprogrammed annealing (TPA) spectra of Ti3+ color centers photoinduced in VLA TiO2 displayed temperature dependencies of the rate of detrapping of the photoinduced holes observed optically through annihilation of the Ti3+ centers. The TPA spectra in the range 90–500 K consisted of a set of first-order peaks corresponding to the traps, whose depths ranged from ∼0.2 eV (peak at 130 K in powder specimen) to 1.06 eV (peak at 455 K in the ceramics). The highest rate of recombination of holes released to the valence band with Ti3+ centers, an event attributable to the Tiδ+ centers, provided TPA spectra that clearly manifested the existence of shallow traps. We also report mass spectrometric evidence of the photoformation of electrons and holes in VLA TiO2 under Vis-light illumination through an examination of the photoadsorption of molecular oxygen and the photodesorption of photoadsorbed oxygen from the surface of powdered VLA titania specimens. Moreover, kinetics of the photodesorption of O2 under orange light illumination, after the photoadsorption of O2 stimulated by blue light excitation, provided experimental proof of the occurrence of an additional specific channel toward the photoactivation of VLA TiO2 via the photoexcitation of photoinduced Ti3+ color centers.",
keywords = "Advanced diffuse reflectance spectroscopy, Color centers, Photoformation of charge carriers, Thermoprogrammed annealing spectra, Visible-light-active rutile titania",
author = "Kuznetsov, {Vyacheslav N.} and Glazkova, {Nadezhda I.} and Mikhaylov, {Ruslan V.} and Kozhevina, {Anna V.} and Nick Serpone",
year = "2020",
month = "1",
day = "15",
doi = "10.1016/j.cattod.2018.09.022",
language = "English",
volume = "340",
pages = "58--69",
journal = "Catalysis Today",
issn = "0920-5861",
publisher = "Elsevier",

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TY - JOUR

T1 - Photophysics of color centers in visible-light-active rutile titania. Evidence of the photoformation and trapping of charge carriers from advanced diffuse reflectance spectroscopy and mass spectrometry

AU - Kuznetsov, Vyacheslav N.

AU - Glazkova, Nadezhda I.

AU - Mikhaylov, Ruslan V.

AU - Kozhevina, Anna V.

AU - Serpone, Nick

PY - 2020/1/15

Y1 - 2020/1/15

N2 - We herein report on the photophysics of color centers in visible-light-active (VLA) rutile titania ceramics and titania powder resulting from the photoformation and separation of charge carriers explored by a diffuse reflectance (DR) spectroscopic and kinetic study using a cryostat-type accessory for a Cary 5000 spectrophotometer after exposure of the titanias to UV radiation and Vis-light illumination. The action spectrum of the photoformation of Ti3+ at 90 K accorded fully with the absorption spectrum of intrinsic defects in the as-synthesized TiO2. The photoinduced absorption spectra consisted of a set of individual absorption bands attributable to several different Ti3+ centers. Analysis of the dependencies of the photoformation of separate centers on the wavelength of illumination and light exposure provided extraction of specific Ti3+ centers putatively attributed to centers with excess negative charge {2Ti3+ + Vo 2+} ⟵→ {Tiδ+ + Vo 2+} with 3 > δ > 2 formed at significantly high concentration upon maximal exposure to Vis-light illumination. Thermoprogrammed annealing (TPA) spectra of Ti3+ color centers photoinduced in VLA TiO2 displayed temperature dependencies of the rate of detrapping of the photoinduced holes observed optically through annihilation of the Ti3+ centers. The TPA spectra in the range 90–500 K consisted of a set of first-order peaks corresponding to the traps, whose depths ranged from ∼0.2 eV (peak at 130 K in powder specimen) to 1.06 eV (peak at 455 K in the ceramics). The highest rate of recombination of holes released to the valence band with Ti3+ centers, an event attributable to the Tiδ+ centers, provided TPA spectra that clearly manifested the existence of shallow traps. We also report mass spectrometric evidence of the photoformation of electrons and holes in VLA TiO2 under Vis-light illumination through an examination of the photoadsorption of molecular oxygen and the photodesorption of photoadsorbed oxygen from the surface of powdered VLA titania specimens. Moreover, kinetics of the photodesorption of O2 under orange light illumination, after the photoadsorption of O2 stimulated by blue light excitation, provided experimental proof of the occurrence of an additional specific channel toward the photoactivation of VLA TiO2 via the photoexcitation of photoinduced Ti3+ color centers.

AB - We herein report on the photophysics of color centers in visible-light-active (VLA) rutile titania ceramics and titania powder resulting from the photoformation and separation of charge carriers explored by a diffuse reflectance (DR) spectroscopic and kinetic study using a cryostat-type accessory for a Cary 5000 spectrophotometer after exposure of the titanias to UV radiation and Vis-light illumination. The action spectrum of the photoformation of Ti3+ at 90 K accorded fully with the absorption spectrum of intrinsic defects in the as-synthesized TiO2. The photoinduced absorption spectra consisted of a set of individual absorption bands attributable to several different Ti3+ centers. Analysis of the dependencies of the photoformation of separate centers on the wavelength of illumination and light exposure provided extraction of specific Ti3+ centers putatively attributed to centers with excess negative charge {2Ti3+ + Vo 2+} ⟵→ {Tiδ+ + Vo 2+} with 3 > δ > 2 formed at significantly high concentration upon maximal exposure to Vis-light illumination. Thermoprogrammed annealing (TPA) spectra of Ti3+ color centers photoinduced in VLA TiO2 displayed temperature dependencies of the rate of detrapping of the photoinduced holes observed optically through annihilation of the Ti3+ centers. The TPA spectra in the range 90–500 K consisted of a set of first-order peaks corresponding to the traps, whose depths ranged from ∼0.2 eV (peak at 130 K in powder specimen) to 1.06 eV (peak at 455 K in the ceramics). The highest rate of recombination of holes released to the valence band with Ti3+ centers, an event attributable to the Tiδ+ centers, provided TPA spectra that clearly manifested the existence of shallow traps. We also report mass spectrometric evidence of the photoformation of electrons and holes in VLA TiO2 under Vis-light illumination through an examination of the photoadsorption of molecular oxygen and the photodesorption of photoadsorbed oxygen from the surface of powdered VLA titania specimens. Moreover, kinetics of the photodesorption of O2 under orange light illumination, after the photoadsorption of O2 stimulated by blue light excitation, provided experimental proof of the occurrence of an additional specific channel toward the photoactivation of VLA TiO2 via the photoexcitation of photoinduced Ti3+ color centers.

KW - Advanced diffuse reflectance spectroscopy

KW - Color centers

KW - Photoformation of charge carriers

KW - Thermoprogrammed annealing spectra

KW - Visible-light-active rutile titania

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DO - 10.1016/j.cattod.2018.09.022

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JO - Catalysis Today

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