Splitting Dioxygen over Distant Binuclear Fe Sites in Zeolites. Effect of the Local Arrangement and Framework Topology

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F21%3A00539845" target="_blank" >RIV/61388955:_____/21:00539845 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/00216275:25310/21:39918009

Výsledek na webu

<a href="http://hdl.handle.net/11104/0317547" target="_blank" >http://hdl.handle.net/11104/0317547</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acscatal.0c04459" target="_blank" >10.1021/acscatal.0c04459</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Splitting Dioxygen over Distant Binuclear Fe Sites in Zeolites. Effect of the Local Arrangement and Framework Topology

Popis výsledku v původním jazyce

Activation of dioxygen is of extreme importance due to its potential for transformation of methane to valuable products and applications in other selective oxidation reactions. Distant binuclear cationic Fe(II) centers in Fe-ferrierite were shown to split dioxygen at room temperature to form a pair of very active oxygen species (i.e., α-oxygens) and subsequently oxidize methane to methanol at room temperature as well. Our study reveals that the activity in splitting dioxygen represents a general property of the distant binuclear cationic Fe(II) centers stabilized in the aluminosilicate matrix. Computational models of the ferrierite, beta, A, and mordenite zeolites with various Al sitings in the rings forming the cationic sites were investigated by periodic DFT calculations including molecular dynamics simulations. The results reveal that the Fe(II) sites stabilized in various zeolite matrices can split dioxygen if the two cationic sites forming the distant binuclear Fe(II) centers (i) face each other, (ii) are parallel, and (iii) are axial, and (iv) the Fe···Fe distance lies in a narrow range from ca. 7 to ca. 8 Å (ca. 7–ca. 10 Å for the distance between the two rings (forming the corresponding cationic sites) in empty zeolites since this distance is equal to or larger than the Fe···Fe distances). Our study opens the possibility of developing Fe-zeolite-based systems for the dioxygen activation employed for direct oxidations using various zeolite matrices.

Název v anglickém jazyce

Splitting Dioxygen over Distant Binuclear Fe Sites in Zeolites. Effect of the Local Arrangement and Framework Topology

Popis výsledku anglicky

Activation of dioxygen is of extreme importance due to its potential for transformation of methane to valuable products and applications in other selective oxidation reactions. Distant binuclear cationic Fe(II) centers in Fe-ferrierite were shown to split dioxygen at room temperature to form a pair of very active oxygen species (i.e., α-oxygens) and subsequently oxidize methane to methanol at room temperature as well. Our study reveals that the activity in splitting dioxygen represents a general property of the distant binuclear cationic Fe(II) centers stabilized in the aluminosilicate matrix. Computational models of the ferrierite, beta, A, and mordenite zeolites with various Al sitings in the rings forming the cationic sites were investigated by periodic DFT calculations including molecular dynamics simulations. The results reveal that the Fe(II) sites stabilized in various zeolite matrices can split dioxygen if the two cationic sites forming the distant binuclear Fe(II) centers (i) face each other, (ii) are parallel, and (iii) are axial, and (iv) the Fe···Fe distance lies in a narrow range from ca. 7 to ca. 8 Å (ca. 7–ca. 10 Å for the distance between the two rings (forming the corresponding cationic sites) in empty zeolites since this distance is equal to or larger than the Fe···Fe distances). Our study opens the possibility of developing Fe-zeolite-based systems for the dioxygen activation employed for direct oxidations using various zeolite matrices.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/GA17-00742S" target="_blank" >GA17-00742S: Binukleární struktury iontů v zeolitech</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2021

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

ACS Catalysis

ISSN

2155-5435

e-ISSN

2155-5435

Svazek periodika

11

Číslo periodika v rámci svazku

4

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

16

Strana od-do

2340-2355

Kód UT WoS článku

000621598700035

EID výsledku v databázi Scopus

2-s2.0-85101027291