The Routes of Association of (Hydro)oxo centers on Iron Hydroxide at the Water Oxidation Process: DFT Predictions
Science article
| Общее |
Language:
Английский,
Genre:
Full article,
Status:
Published,
Source type:
Original
|
| Journal |
Chemical Physics Letters
ISSN: 0009-2614
, E-ISSN: 1873-4448
|
| Output data |
Year: 2015,
Volume: 619,
Pages: 126-132
Pages count
: 7
DOI:
10.1016/j.cplett.2014.11.061
|
| Authors |
Shubin Aleksandr A.
1
,
Ruzankin Sergey Ph.
1
,
Zilberberg Igor L.
1
,
Taran Oxana P.
1
,
Parmon Valentin N.
1
|
| Affiliations |
| 1 |
Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Prospekt Akademika Lavrentieva 5, Novosibirsk 630090, Russia
|
|
Funding (1)
|
1
|
Russian Science Foundation
|
14-13-01155
|
The formation of the Osingle bondO bond in the water oxidation catalyzed by the iron hydroxides was modeled with the Fe4O4(OH)4 and Fe2O2(OH)4 complexes by means of the density functional theory. Consideration of the local minima and transition states for various routes of the association of oxo- and hydroxo-centers reveals a determinative role of the oxyl radical center FeIIIsingle bondOradical dot− in facilitating this process. The preferable scenario comprises two steps: (1) the abstraction of the electron and proton from the initial complex leaving behind a ferryl FeO group, and (2) the incorporation of ferryl oxygen into the tetramer edge to form peroxo group.