Anionic or Cationic S-Doping in Bulk Anatase TiO 2 : Insights on Optical Absorption from First Principles Calculations

Handle URI:
http://hdl.handle.net/10754/594277
Title:
Anionic or Cationic S-Doping in Bulk Anatase TiO 2 : Insights on Optical Absorption from First Principles Calculations
Authors:
Harb, Moussab ( 0000-0001-5540-9792 ) ; Sautet, P.; Raybaud, P.
Abstract:
Using first principles calculations, we investigate the structural, electronic, optical, and energetic properties of S-doped anatase TiO2 bulk systems. To ensure accurate band gap predictions, we use the HSE06 exchange correlation functional, and the absorption spectra are obtained with density functional perturbation (DFPT) theory by employing HSE06. Various oxidation states (anionic and cationic) of sulfur are considered depending on the location in bulk TiO2: in interstitial position or in substitution for either oxygen or titanium atoms. Among the explored structures, two anionic and one cationic configurations induce an improved optical absorption response in the visible region as observed experimentally. Moreover, we undertake a thermodynamic analysis as a function of the chemical potential of oxygen and considering three relevant sulfur chemical doping agents (S 2, H2S, and thiourea). It highlights that cationic configurations (S4+ and S6+) are strongly stabilized in a wide range of oxygen chemical potential (including standard conditions), whereas anionic species are stabilized only at very low chemical potential of oxygen. The metastable cationic Ti(1-2x)O2S2x system involving the presence of S4+ species in substitution for Ti 4+, with the formation of SO2 units, should offer the best compromise between the thermodynamic conditions and the expected optical properties. © 2013 American Chemical Society.
KAUST Department:
KAUST Catalysis Center (KCC)
Citation:
Harb M, Sautet P, Raybaud P (2013) Anionic or Cationic S-Doping in Bulk Anatase TiO 2 : Insights on Optical Absorption from First Principles Calculations . The Journal of Physical Chemistry C 117: 8892–8902. Available: http://dx.doi.org/10.1021/jp312197g.
Publisher:
American Chemical Society (ACS)
Journal:
The Journal of Physical Chemistry C
Issue Date:
2-May-2013
DOI:
10.1021/jp312197g
Type:
Article
ISSN:
1932-7447; 1932-7455
Sponsors:
This work was supported by Award No. UK-C0017, made by King Abdullah University of Science and Technology (KAUST).
Appears in Collections:
Articles; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorHarb, Moussaben
dc.contributor.authorSautet, P.en
dc.contributor.authorRaybaud, P.en
dc.date.accessioned2016-01-19T14:45:01Zen
dc.date.available2016-01-19T14:45:01Zen
dc.date.issued2013-05-02en
dc.identifier.citationHarb M, Sautet P, Raybaud P (2013) Anionic or Cationic S-Doping in Bulk Anatase TiO 2 : Insights on Optical Absorption from First Principles Calculations . The Journal of Physical Chemistry C 117: 8892–8902. Available: http://dx.doi.org/10.1021/jp312197g.en
dc.identifier.issn1932-7447en
dc.identifier.issn1932-7455en
dc.identifier.doi10.1021/jp312197gen
dc.identifier.urihttp://hdl.handle.net/10754/594277en
dc.description.abstractUsing first principles calculations, we investigate the structural, electronic, optical, and energetic properties of S-doped anatase TiO2 bulk systems. To ensure accurate band gap predictions, we use the HSE06 exchange correlation functional, and the absorption spectra are obtained with density functional perturbation (DFPT) theory by employing HSE06. Various oxidation states (anionic and cationic) of sulfur are considered depending on the location in bulk TiO2: in interstitial position or in substitution for either oxygen or titanium atoms. Among the explored structures, two anionic and one cationic configurations induce an improved optical absorption response in the visible region as observed experimentally. Moreover, we undertake a thermodynamic analysis as a function of the chemical potential of oxygen and considering three relevant sulfur chemical doping agents (S 2, H2S, and thiourea). It highlights that cationic configurations (S4+ and S6+) are strongly stabilized in a wide range of oxygen chemical potential (including standard conditions), whereas anionic species are stabilized only at very low chemical potential of oxygen. The metastable cationic Ti(1-2x)O2S2x system involving the presence of S4+ species in substitution for Ti 4+, with the formation of SO2 units, should offer the best compromise between the thermodynamic conditions and the expected optical properties. © 2013 American Chemical Society.en
dc.description.sponsorshipThis work was supported by Award No. UK-C0017, made by King Abdullah University of Science and Technology (KAUST).en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleAnionic or Cationic S-Doping in Bulk Anatase TiO 2 : Insights on Optical Absorption from First Principles Calculationsen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.identifier.journalThe Journal of Physical Chemistry Cen
dc.contributor.institutionIFP Energies Nouvelles, Rond-point de l'Échangeur de Solaize, BP 3, 69360 Solaize, Franceen
dc.contributor.institutionUniversité de Lyon, CNRS, Ecole Normale Supérieure de Lyon, 46 allée d'Italie, 69364 Lyon cedex 07, Franceen
kaust.authorHarb, Moussaben
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