Anatase nanoparticles surface modified with fused ring salicylate-type ligands (1-hydroxy-2-naphthoic acids): A combined DFT and experimental study
Само за регистроване кориснике
2015
Аутори
Savić, Tatjana D.Čomor, Mirjana I.
Abazović, Nadica D.
Šaponjić, Zoran V.
Marinović-Cincović, Milena T.
Veljković, Dušan Ž.
Zarić, Snežana D.
Janković, Ivana A.
Чланак у часопису (Објављена верзија)
Метаподаци
Приказ свих података о документуАпстракт
Sensitization of TiO2 crystals and nanoparticles with appropriately chosen organic molecules can lead to a significant shift of their absorption threshold from the UV to the visible, thus improving the absorption of the solar spectrum as well as the efficiency of photocatalytic and photovoltaic devices. Herein, the surface modification of nanocrystalline TiO2 particles (45 angstrom) with salicylate-type ligands consisting of an extended aromatic ring system, specifically 1-hydroxy-2-naphthoic acid and 1,4-dihydroxy-2-naphthoic acid, was found to alter the optical properties of nanoparticles in a similar way to salicylic acid. From both absorption measurements and steady-state quenching measurements of modifier fluorescence upon binding to TiO2 in methanol/ water = 90/10 solutions, stability constants in the order of 10(3) M-1 have been determined at pH 2. Fluorescence lifetime measurements, in the presence and absence of colloidal TiO2 nanoparticles, indicated that the fluorescence que...nching process is primarily static quenching, thus proving the formation of a nonfluorescent charge-transfer (CT) complex. The binding structures were investigated by using FTIR spectroscopy. Thermal stability of CT-complexes was investigated by using TPD analysis (TG/DTA/MS). 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 compared with the experimental data. 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. The formation of the inner-sphere 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.
Кључне речи:
TiO2 nanoparticles / Charge-transfer (CT) complex / Salicylic acid / 1-Hydroxy-2-naphthoic acid / 1,4-Dihydroxy-2-naphthoic acid / Density functional theory (DFT)Извор:
Journal of Alloys and Compounds, 2015, 630, 226-235Издавач:
- Elsevier Science Sa, Lausanne
Финансирање / пројекти:
- Утицај величине, облика и структуре наночестица на њихова својства и својства нанокомпозита (RS-172056)
- Материјали редуковане димензионалности за ефикасну апсорпцију светлости и конверзију енергије (RS-45020)
Напомена:
- Supplementary material: http://cherry.chem.bg.ac.rs/handle/123456789/3337
DOI: 10.1016/j.jallcom.2015.01.041
ISSN: 0925-8388
WoS: 000349706800034
Scopus: 2-s2.0-84921922110
Колекције
Институција/група
Hemijski fakultet / Faculty of ChemistryTY - JOUR AU - Savić, Tatjana D. AU - Čomor, Mirjana I. AU - Abazović, Nadica D. AU - Šaponjić, Zoran V. AU - Marinović-Cincović, Milena T. AU - Veljković, Dušan Ž. AU - Zarić, Snežana D. AU - Janković, Ivana A. PY - 2015 UR - https://cherry.chem.bg.ac.rs/handle/123456789/1661 AB - Sensitization of TiO2 crystals and nanoparticles with appropriately chosen organic molecules can lead to a significant shift of their absorption threshold from the UV to the visible, thus improving the absorption of the solar spectrum as well as the efficiency of photocatalytic and photovoltaic devices. Herein, the surface modification of nanocrystalline TiO2 particles (45 angstrom) with salicylate-type ligands consisting of an extended aromatic ring system, specifically 1-hydroxy-2-naphthoic acid and 1,4-dihydroxy-2-naphthoic acid, was found to alter the optical properties of nanoparticles in a similar way to salicylic acid. From both absorption measurements and steady-state quenching measurements of modifier fluorescence upon binding to TiO2 in methanol/ water = 90/10 solutions, stability constants in the order of 10(3) M-1 have been determined at pH 2. 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 charge-transfer (CT) complex. The binding structures were investigated by using FTIR spectroscopy. Thermal stability of CT-complexes was investigated by using TPD analysis (TG/DTA/MS). 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 compared with the experimental data. 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. The formation of the inner-sphere 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. PB - Elsevier Science Sa, Lausanne T2 - Journal of Alloys and Compounds T1 - Anatase nanoparticles surface modified with fused ring salicylate-type ligands (1-hydroxy-2-naphthoic acids): A combined DFT and experimental study VL - 630 SP - 226 EP - 235 DO - 10.1016/j.jallcom.2015.01.041 ER -
@article{ author = "Savić, Tatjana D. and Čomor, Mirjana I. and Abazović, Nadica D. and Šaponjić, Zoran V. and Marinović-Cincović, Milena T. and Veljković, Dušan Ž. and Zarić, Snežana D. and Janković, Ivana A.", year = "2015", abstract = "Sensitization of TiO2 crystals and nanoparticles with appropriately chosen organic molecules can lead to a significant shift of their absorption threshold from the UV to the visible, thus improving the absorption of the solar spectrum as well as the efficiency of photocatalytic and photovoltaic devices. Herein, the surface modification of nanocrystalline TiO2 particles (45 angstrom) with salicylate-type ligands consisting of an extended aromatic ring system, specifically 1-hydroxy-2-naphthoic acid and 1,4-dihydroxy-2-naphthoic acid, was found to alter the optical properties of nanoparticles in a similar way to salicylic acid. From both absorption measurements and steady-state quenching measurements of modifier fluorescence upon binding to TiO2 in methanol/ water = 90/10 solutions, stability constants in the order of 10(3) M-1 have been determined at pH 2. 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 charge-transfer (CT) complex. The binding structures were investigated by using FTIR spectroscopy. Thermal stability of CT-complexes was investigated by using TPD analysis (TG/DTA/MS). 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 compared with the experimental data. 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. The formation of the inner-sphere 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.", publisher = "Elsevier Science Sa, Lausanne", journal = "Journal of Alloys and Compounds", title = "Anatase nanoparticles surface modified with fused ring salicylate-type ligands (1-hydroxy-2-naphthoic acids): A combined DFT and experimental study", volume = "630", pages = "226-235", doi = "10.1016/j.jallcom.2015.01.041" }
Savić, T. D., Čomor, M. I., Abazović, N. D., Šaponjić, Z. V., Marinović-Cincović, M. T., Veljković, D. Ž., Zarić, S. D.,& Janković, I. A.. (2015). Anatase nanoparticles surface modified with fused ring salicylate-type ligands (1-hydroxy-2-naphthoic acids): A combined DFT and experimental study. in Journal of Alloys and Compounds Elsevier Science Sa, Lausanne., 630, 226-235. https://doi.org/10.1016/j.jallcom.2015.01.041
Savić TD, Čomor MI, Abazović ND, Šaponjić ZV, Marinović-Cincović MT, Veljković DŽ, Zarić SD, Janković IA. Anatase nanoparticles surface modified with fused ring salicylate-type ligands (1-hydroxy-2-naphthoic acids): A combined DFT and experimental study. in Journal of Alloys and Compounds. 2015;630:226-235. doi:10.1016/j.jallcom.2015.01.041 .
Savić, Tatjana D., Čomor, Mirjana I., Abazović, Nadica D., Šaponjić, Zoran V. , Marinović-Cincović, Milena T., Veljković, Dušan Ž., Zarić, Snežana D., Janković, Ivana A., "Anatase nanoparticles surface modified with fused ring salicylate-type ligands (1-hydroxy-2-naphthoic acids): A combined DFT and experimental study" in Journal of Alloys and Compounds, 630 (2015):226-235, https://doi.org/10.1016/j.jallcom.2015.01.041 . .