Oxygen Atom Exchange between Gaseous CO2 and TiO2 Nanoclusters

0446907 - ÚFCH JH 2016 RIV US eng J - Článek v odborném periodiku
Civiš, Svatopluk - Ferus, Martin - Zukalová, Markéta - Zukal, Arnošt - Kavan, Ladislav - Jordan, K. D. - Sorescu, D. C.
Oxygen Atom Exchange between Gaseous CO2 and TiO2 Nanoclusters.
Journal of Physical Chemistry C. Roč. 119, č. 7 (2015), s. 3605-3612. ISSN 1932-7447. E-ISSN 1932-7455
Grant CEP: GA ČR GA13-07724S; GA ČR(CZ) GAP108/12/0814; GA MŠMT(CZ) LD13060; GA MŠMT LD14115
Grant ostatní: COST(XE) CM1104
Institucionální podpora: RVO:61388955
Klíčová slova: TiO2 * carbon dioxide * nanoparticles
Kód oboru RIV: CF - Fyzikální chemie a teoretická chemie
Impakt faktor: 4.509, rok: 2015

Isotopic exchange of oxygen atoms between gaseous (CO2)-O-18 and (TiO2)-O-16 nanoparticles has been studied using high-resolution Fourier transform infrared absorption and first-principles density functional theory calculations. The rate of formation of gaseous (CO2)-O-16 is found to be highly dependent on the nature of the titania sample, growing with increasing calcination temperature (i.e., with decreasing surface area) for both quasi-amorphous and crystalline samples. The unprecedented faster kinetics on high-surface-area titania made from Ti(IV) isopropoxide points at fundamental differences between this material and the usual nanocrystalline TiO2 (anatase). This is attributed to unique cluster-like structure of the noncalcined ex-isopropoxide titania. The experimental observations are rationalized by calculations of the activation barriers for oxygen exchange on a (TiO2)(10) cluster. The calculations predict that titanium nanoclusters with 4-fold coordinated titanium atoms have much lower barriers for O atom exchange than previously found for the oxygen defect sites on the single crystal (101) anatase surface.
Trvalý link: http://hdl.handle.net/11104/0248871