Browsing by Author "Chang, Ching Yi"

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Adsorption Configurations and Reactions of Nitric Acid on TiO(2) Rutile (110) and Anatase (101) surfaces
(2009-04-16)
Chang, Ching Yi
;
Chen, Hsin-Tsung
;
Lin, M. C.
;
應用化學系分子科學碩博班
;
Institute of Molecular science
The adsorption and reactions of the monomer and dimer of nitric acid on TiO(2) rutile (110) and anatase (101) surfaces have been studied by first-principles density functional theory with ultrasoft pseudopotential approximation. The most stable configuration of HNO(3) on the rutile surface is a molecular monodentate adsorbed on the 5-fold coordinated Ti atom with the hydrogen bonded to a neighboring surface bridging oxygen with the adsorption energy of 6.7 kcal/mol. It can dissociate its H atom to a nearest bridged oxygen with almost no barrier to produce NO(3)(a) + H(a). The rotation of NO(3) requires a barrier of 12.2 kcal/mol to form the didentate configuration, Ti(5c)-ON(O)-Ti(5c)H-O(2),(a), which adsorbs on two 5-fold coordinated Ti atoms with the adsorption energy of 16.5 kcal/mol. In the case of the adsorption of 2HNO(3) molecules, the most stable configuration, 2(Ti(5c)-ON(O)OH...O(2c)(a)), has a structure similar to two single HNO(3) adsorbates on two 5-fold coordinated Ti atoms with the adsorption energy of 12.8 kcal/mol, which is about twice that of the single HNO(3) molecule. The result suggests that the interaction of the two planar HNO(3) adsorbates is negligible. The dehydration from 2(Ti(5c)-ON(O)OH...O(2)c(a)) forming N(2)O(5)(a) + H(2)O(a) requires an energy barrier of 46.2 kcal/mol, indicating that the dimerization of the two HNO(3)(a) is difficult. Similar adsorption phenomena appear on the anatase (101) surface. In addition, we find that the coadsorption of hydrogen plays a significant role in the adsorption energies of adsorbates, especially for the NO(3) radical, which may be employed as a linker between semiconductor quantum dots such as InN and the TiO(2) surface.
Adsorption Configurations and Reactions of Nitric Acid on TiO2 Rutile (110) and Anatase (101) surfaces
(2009-04-16)
Chang, Ching Yi
;
Chen, Hsin-Tsung
;
Lin, M. C.
;
應用化學系分子科學碩博班
;
Institute of Molecular science
The adsorption and reactions of the monomer and dimer of nitric acid on TiO2 rutile (110) and anatase (101) surfaces have been studied by first-principles density functional theory with ultrasoft pseudopotential approximation. The most stable configuration of HNO3 on the rutile surface is a molecular monodentate adsorbed on the 5-fold coordinated Ti atom with the hydrogen bonded to a neighboring surface bridging oxygen with the adsorption energy of 6.7 kcal/mol. It can dissociate its H atom to a nearest bridged oxygen with almost no barrier to produce NO3(a) + H(a). The rotation of NO3 requires a barrier of 12.2 kcal/mol to form the didentate configuration, Ti-5c-ON(O)-Ti5cH-O-2,(a), which adsorbs on two 5-fold coordinated Ti atoms with the adsorption energy of 16.5 kcal/mol. In the case of the adsorption of 2HNO(3) molecules, the most stable configuration, 2(Ti-5c-ON(O)OH...O-2c(a)), has a structure similar to two single HNO3 adsorbates on two 5-fold coordinated Ti atoms with the adsorption energy of 12.8 kcal/mol, which is about twice that of the single HNO3 molecule. The result suggests that the interaction of the two planar HNO3 adsorbates is negligible. The dehydration from 2(Ti-5c-ON(O)OH...O(2)c(a)) forming N2O5(a) + H2O(a) requires an energy barrier of 46.2 kcal/mol, indicating that the dimerization of the two HNO3(a) is difficult. Similar adsorption phenomena appear on the anatase (101) surface. In addition, we find that the coadsorption of hydrogen plays a significant role in the adsorption energies of adsorbates, especially for the NO3 radical, which may be employed as a linker between semiconductor quantum dots such as InN and the TiO2 surface.