Abstract
Salicylate and salicylic acid derivatives act as electron donors via charge-transfer complexes when adsorbed on semiconducting surfaces. When photoexcited, charge is injected into the conduction band directly from their highest occupied molecular orbital (HOMO) without needing mediation by the lowest unoccupied molecular orbital (LUMO). In this study, we successfully induce the chemical participation of carbon dioxide in a charge transfer state using 3-aminosalicylic acid (3ASA). We determine the geometry of CO2 using a combination of ultraviolet-visible spectroscopy (UV-vis), surface enhanced Raman scattering (SERS), 13C NMR, and electron paramagnetic resonance (EPR). We find CO2 binds on Ti sites in a carbonate form and discern via EPR a surface Ti-centered radical in the vicinity of CO 2, suggesting successful charge transfer from the sensitizer to the neighboring site of CO2. This study opens the possibility of analyzing the structural and electronic properties of the anchoring sites for CO2 on semiconducting surfaces and proposes a set of tools and experiments to do so.
| Original language | English |
|---|---|
| Pages (from-to) | 475-479 |
| Number of pages | 5 |
| Journal | Journal of Physical Chemistry Letters |
| Volume | 4 |
| Issue number | 3 |
| DOIs | |
| Publication status | Published - Feb 7 2013 |
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Keywords
- catechol
- charge-transfer
- CO activation
- SERS
- TiO
ASJC Scopus subject areas
- Materials Science(all)
Cite this
CO2 preactivation in photoinduced reduction via surface functionalization of TiO2 nanoparticles. / Finkelstein-Shapiro, Daniel; Petrosko, Sarah Hurst; Dimitrijevic, Nada M.; Gosztola, David; Gray, Kimberly A.; Rajh, Tijana; Tarakeshwar, Pilarisetty; Mujica, Vladimiro.
In: Journal of Physical Chemistry Letters, Vol. 4, No. 3, 07.02.2013, p. 475-479.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - CO2 preactivation in photoinduced reduction via surface functionalization of TiO2 nanoparticles
AU - Finkelstein-Shapiro, Daniel
AU - Petrosko, Sarah Hurst
AU - Dimitrijevic, Nada M.
AU - Gosztola, David
AU - Gray, Kimberly A.
AU - Rajh, Tijana
AU - Tarakeshwar, Pilarisetty
AU - Mujica, Vladimiro
PY - 2013/2/7
Y1 - 2013/2/7
N2 - Salicylate and salicylic acid derivatives act as electron donors via charge-transfer complexes when adsorbed on semiconducting surfaces. When photoexcited, charge is injected into the conduction band directly from their highest occupied molecular orbital (HOMO) without needing mediation by the lowest unoccupied molecular orbital (LUMO). In this study, we successfully induce the chemical participation of carbon dioxide in a charge transfer state using 3-aminosalicylic acid (3ASA). We determine the geometry of CO2 using a combination of ultraviolet-visible spectroscopy (UV-vis), surface enhanced Raman scattering (SERS), 13C NMR, and electron paramagnetic resonance (EPR). We find CO2 binds on Ti sites in a carbonate form and discern via EPR a surface Ti-centered radical in the vicinity of CO 2, suggesting successful charge transfer from the sensitizer to the neighboring site of CO2. This study opens the possibility of analyzing the structural and electronic properties of the anchoring sites for CO2 on semiconducting surfaces and proposes a set of tools and experiments to do so.
AB - Salicylate and salicylic acid derivatives act as electron donors via charge-transfer complexes when adsorbed on semiconducting surfaces. When photoexcited, charge is injected into the conduction band directly from their highest occupied molecular orbital (HOMO) without needing mediation by the lowest unoccupied molecular orbital (LUMO). In this study, we successfully induce the chemical participation of carbon dioxide in a charge transfer state using 3-aminosalicylic acid (3ASA). We determine the geometry of CO2 using a combination of ultraviolet-visible spectroscopy (UV-vis), surface enhanced Raman scattering (SERS), 13C NMR, and electron paramagnetic resonance (EPR). We find CO2 binds on Ti sites in a carbonate form and discern via EPR a surface Ti-centered radical in the vicinity of CO 2, suggesting successful charge transfer from the sensitizer to the neighboring site of CO2. This study opens the possibility of analyzing the structural and electronic properties of the anchoring sites for CO2 on semiconducting surfaces and proposes a set of tools and experiments to do so.
KW - catechol
KW - charge-transfer
KW - CO activation
KW - SERS
KW - TiO
UR - http://www.scopus.com/inward/record.url?scp=84873465718&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84873465718&partnerID=8YFLogxK
U2 - 10.1021/jz3020327
DO - 10.1021/jz3020327
M3 - Article
AN - SCOPUS:84873465718
VL - 4
SP - 475
EP - 479
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
SN - 1948-7185
IS - 3
ER -