Surface modification of anatase nanoparticles with fused ring salicylate-type ligands (3-hydroxy-2-naphthoic acids): a combined DFT and experimental study of optical properties
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Savić, Tatjana D.Šaponjić, Zoran
Čomor, Mirjana
Nedeljković, Jovan
Dramićanin, Miroslav
Nikolić, Marko G.
Veljkovic, Dusan Z.
Zarić, Snežana D.
Janković, Ivana A.
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The surface modification of nanocrystalline TiO2 particles (45 angstrom) with salicylate-type ligands consisting of an extended aromatic ring system, specifically 3-hydroxy-2-naphthoic acid, 3,5-dihydroxy-2-naphthoic acid and 3,7-dihydroxy-2-naphthoic acid, was found to alter the optical properties of nanoparticles in a similar way to salicylic acid. The formation of the inner-sphere charge-transfer (CT) complexes results in a red shift of the semiconductor absorption compared to unmodified nanocrystallites and a reduction in the band gap upon the increase in the electron delocalization when including an additional ring. The investigated ligands have the optimal geometry for binding to surface Ti atoms, resulting in ring coordination complexes of a salicylate-type (binuclear bidentate binding-bridging) thus restoring the six-coordinated octahedral geometry of surface Ti atoms. From both absorption measurements in methanol/water = 90/10 solutions and steady-state quenching measurements ...of modifier fluorescence upon binding to TiO2 in aqueous solutions, stability constants in the order of 10(3) M-1 have been determined at pH 2 and pH 3. Fluorescence lifetime measurements, in the presence and absence of colloidal TiO2 nanoparticles, indicated that the fluorescence quenching process is primarily static quenching, thus proving the formation of a nonfluorescent CT complex. The binding structures were investigated by using FTIR spectroscopy. Quantum chemical calculations on model systems using density functional theory (DFT) were performed to obtain the vibrational frequencies of charge transfer complexes, and the calculated values were then compared with the experimental data.
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Nanoscale, 2013, 5, 16, 7601-7612Funding / projects:
- Materials of Reduced Dimensions for Efficient Light Harvesting and Energy conversion (RS-MESTD-Integrated and Interdisciplinary Research (IIR or III)-45020)
- Size-, shape- and structure- dependent properties of nanoparticles and nanocomposites (RS-MESTD-Basic Research (BR or ON)-172056)
DOI: 10.1039/c3nr01277h
ISSN: 2040-3364
PubMed: 23842592
WoS: 000322315600065
Scopus: 2-s2.0-84880914973
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VinčaTY - JOUR AU - Savić, Tatjana D. AU - Šaponjić, Zoran AU - Čomor, Mirjana AU - Nedeljković, Jovan AU - Dramićanin, Miroslav AU - Nikolić, Marko G. AU - Veljkovic, Dusan Z. AU - Zarić, Snežana D. AU - Janković, Ivana A. PY - 2013 UR - https://vinar.vin.bg.ac.rs/handle/123456789/5601 AB - The surface modification of nanocrystalline TiO2 particles (45 angstrom) with salicylate-type ligands consisting of an extended aromatic ring system, specifically 3-hydroxy-2-naphthoic acid, 3,5-dihydroxy-2-naphthoic acid and 3,7-dihydroxy-2-naphthoic acid, was found to alter the optical properties of nanoparticles in a similar way to salicylic acid. The formation of the inner-sphere charge-transfer (CT) complexes results in a red shift of the semiconductor absorption compared to unmodified nanocrystallites and a reduction in the band gap upon the increase in the electron delocalization when including an additional ring. The investigated ligands have the optimal geometry for binding to surface Ti atoms, resulting in ring coordination complexes of a salicylate-type (binuclear bidentate binding-bridging) thus restoring the six-coordinated octahedral geometry of surface Ti atoms. From both absorption measurements in methanol/water = 90/10 solutions and steady-state quenching measurements of modifier fluorescence upon binding to TiO2 in aqueous solutions, stability constants in the order of 10(3) M-1 have been determined at pH 2 and pH 3. Fluorescence lifetime measurements, in the presence and absence of colloidal TiO2 nanoparticles, indicated that the fluorescence quenching process is primarily static quenching, thus proving the formation of a nonfluorescent CT complex. The binding structures were investigated by using FTIR spectroscopy. Quantum chemical calculations on model systems using density functional theory (DFT) were performed to obtain the vibrational frequencies of charge transfer complexes, and the calculated values were then compared with the experimental data. T2 - Nanoscale T1 - Surface modification of anatase nanoparticles with fused ring salicylate-type ligands (3-hydroxy-2-naphthoic acids): a combined DFT and experimental study of optical properties VL - 5 IS - 16 SP - 7601 EP - 7612 DO - 10.1039/c3nr01277h ER -
@article{ author = "Savić, Tatjana D. and Šaponjić, Zoran and Čomor, Mirjana and Nedeljković, Jovan and Dramićanin, Miroslav and Nikolić, Marko G. and Veljkovic, Dusan Z. and Zarić, Snežana D. and Janković, Ivana A.", year = "2013", abstract = "The surface modification of nanocrystalline TiO2 particles (45 angstrom) with salicylate-type ligands consisting of an extended aromatic ring system, specifically 3-hydroxy-2-naphthoic acid, 3,5-dihydroxy-2-naphthoic acid and 3,7-dihydroxy-2-naphthoic acid, was found to alter the optical properties of nanoparticles in a similar way to salicylic acid. The formation of the inner-sphere charge-transfer (CT) complexes results in a red shift of the semiconductor absorption compared to unmodified nanocrystallites and a reduction in the band gap upon the increase in the electron delocalization when including an additional ring. The investigated ligands have the optimal geometry for binding to surface Ti atoms, resulting in ring coordination complexes of a salicylate-type (binuclear bidentate binding-bridging) thus restoring the six-coordinated octahedral geometry of surface Ti atoms. From both absorption measurements in methanol/water = 90/10 solutions and steady-state quenching measurements of modifier fluorescence upon binding to TiO2 in aqueous solutions, stability constants in the order of 10(3) M-1 have been determined at pH 2 and pH 3. Fluorescence lifetime measurements, in the presence and absence of colloidal TiO2 nanoparticles, indicated that the fluorescence quenching process is primarily static quenching, thus proving the formation of a nonfluorescent CT complex. The binding structures were investigated by using FTIR spectroscopy. Quantum chemical calculations on model systems using density functional theory (DFT) were performed to obtain the vibrational frequencies of charge transfer complexes, and the calculated values were then compared with the experimental data.", journal = "Nanoscale", title = "Surface modification of anatase nanoparticles with fused ring salicylate-type ligands (3-hydroxy-2-naphthoic acids): a combined DFT and experimental study of optical properties", volume = "5", number = "16", pages = "7601-7612", doi = "10.1039/c3nr01277h" }
Savić, T. D., Šaponjić, Z., Čomor, M., Nedeljković, J., Dramićanin, M., Nikolić, M. G., Veljkovic, D. Z., Zarić, S. D.,& Janković, I. A.. (2013). Surface modification of anatase nanoparticles with fused ring salicylate-type ligands (3-hydroxy-2-naphthoic acids): a combined DFT and experimental study of optical properties. in Nanoscale, 5(16), 7601-7612. https://doi.org/10.1039/c3nr01277h
Savić TD, Šaponjić Z, Čomor M, Nedeljković J, Dramićanin M, Nikolić MG, Veljkovic DZ, Zarić SD, Janković IA. Surface modification of anatase nanoparticles with fused ring salicylate-type ligands (3-hydroxy-2-naphthoic acids): a combined DFT and experimental study of optical properties. in Nanoscale. 2013;5(16):7601-7612. doi:10.1039/c3nr01277h .
Savić, Tatjana D., Šaponjić, Zoran, Čomor, Mirjana, Nedeljković, Jovan, Dramićanin, Miroslav, Nikolić, Marko G., Veljkovic, Dusan Z., Zarić, Snežana D., Janković, Ivana A., "Surface modification of anatase nanoparticles with fused ring salicylate-type ligands (3-hydroxy-2-naphthoic acids): a combined DFT and experimental study of optical properties" in Nanoscale, 5, no. 16 (2013):7601-7612, https://doi.org/10.1039/c3nr01277h . .