Proximity Effect on the Reactivity of Dioxygen Activated over Distant Binuclear Fe Sites in Zeolite Matrices
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F22%3A00555822" target="_blank" >RIV/61388955:_____/22:00555822 - isvavai.cz</a>
Result on the web
<a href="http://hdl.handle.net/11104/0330275" target="_blank" >http://hdl.handle.net/11104/0330275</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.jpcc.1c10821" target="_blank" >10.1021/acs.jpcc.1c10821</a>
Alternative languages
Result language
angličtina
Original language name
Proximity Effect on the Reactivity of Dioxygen Activated over Distant Binuclear Fe Sites in Zeolite Matrices
Original language description
Distant binuclear cationic M(II) centers in transition-metal-exchanged zeolites were shown to activate dioxygen by its splitting at room temperature to form a pair of very active oxygen species (i.e., α-oxygens) able to subsequently oxidize methane to methanol at room temperature. Selective oxidations of methane and other hydrocarbons are of extreme importance because of their potential for the transformation of hydrocarbons to valuable products. The reactivity of the α-oxygens with dihydrogen was investigated to obtain insight into the reactivity of these unique species. The reduction of Fe(IV) O centers of pairs of distant α-oxygen atoms is a model reaction that allows for the study of the effect of the proximity of the other Fe(IV) O site on the reactivity of the α-oxygen. The reduction by dihydrogen is also the key reaction for the quantification of these unique sites by temperature-programmed reduction (TPR) techniques. Our study reveals that (i) there is no direct concurrent reaction of both the Fe(IV) O centers of pairs of the distant α-oxygen atoms with a molecule of dihydrogen, (ii) first, one Fe(IV) O site of a pair of the distant α-oxygen atoms reacts with H2(g) to form a water molecule, which is adsorbed on the Fe(II) cation while the other Fe(IV) O site is intact. Afterward, one of the two H atoms of the adsorbed water molecule migrates to yield two Fe(III)OH groups, which subsequently react with another molecule of dihydrogen to give two water molecules, each adsorbed on one Fe(II) cation, (iii) an isolated Fe(IV) O site is reduced by the same mechanism as the first Fe(IV) O site of a pair of the distant α-oxygen atoms to yield H2O adsorbed on the Fe(II) cation, and (iv) lower reducibility of the Fe(IV) O centers of pairs of the distant α-oxygen atoms with respect to the isolated Fe(IV) O sites.
Czech name
—
Czech description
—
Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
—
OECD FORD branch
10403 - Physical chemistry
Result continuities
Project
Result was created during the realization of more than one project. More information in the Projects tab.
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2022
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Journal of Physical Chemistry C
ISSN
1932-7447
e-ISSN
1932-7455
Volume of the periodical
126
Issue of the periodical within the volume
10
Country of publishing house
US - UNITED STATES
Number of pages
8
Pages from-to
4854-4861
UT code for WoS article
000776247200014
EID of the result in the Scopus database
2-s2.0-85126091546