TY - JOUR

T1 - Theoretical investigation of Fe and Cu cations hosted within the MOR zeolite framework

AU - Antúnez-García, Joel

AU - Ponce-Ruiz, Jesus I.A.

AU - Núñez-González, Roberto

AU - Petranovskii, Vitalii

AU - Murrieta-Rico, Fabian N.

AU - Serrato, Armando Reyes

AU - Shelyapina, Marina G.

AU - Xiao, Mufei

AU - Zamora, Jonathan

PY - 2024/12/1

Y1 - 2024/12/1

N2 - Periodic Density Functional Theory (DFT) calculations were used to determine the preferred localization sites of Fe2+ and Cu2+ exchangeable cations in mordenite zeolite. The results revealed that a single Fe2+ ion preferred to occupy the main channel, whereas Cu2+ ion chosen to inhabit the secondary channel. When both Fe2+ and Cu2+ ions were simultaneously present in the zeolite (bimetallic material), both cations were maximally separated within the unit cell. Notably, the iron cation was embedded in a six-membered ring (6MR) with an α-Fe configuration (FeIIO4 unit), which is observed experimentally in many zeolites; this structure was formed despite the fact that, unlike many other zeolites, in mordenite the 6MR ring contains only one Al ion. Additionally, to evaluate the stability of α-Fe, a hydroxyl radical was introduced into the system to interact directly with the iron ion. The results show that in the absence of Cu2+, iron ion Fe2+ is oxidized to Fe3+. However, when Cu2+ is present in the zeolite framework, the coordination of iron with 6MR is preserved despite the formation of a bond with the hydroxyl radical.

AB - Periodic Density Functional Theory (DFT) calculations were used to determine the preferred localization sites of Fe2+ and Cu2+ exchangeable cations in mordenite zeolite. The results revealed that a single Fe2+ ion preferred to occupy the main channel, whereas Cu2+ ion chosen to inhabit the secondary channel. When both Fe2+ and Cu2+ ions were simultaneously present in the zeolite (bimetallic material), both cations were maximally separated within the unit cell. Notably, the iron cation was embedded in a six-membered ring (6MR) with an α-Fe configuration (FeIIO4 unit), which is observed experimentally in many zeolites; this structure was formed despite the fact that, unlike many other zeolites, in mordenite the 6MR ring contains only one Al ion. Additionally, to evaluate the stability of α-Fe, a hydroxyl radical was introduced into the system to interact directly with the iron ion. The results show that in the absence of Cu2+, iron ion Fe2+ is oxidized to Fe3+. However, when Cu2+ is present in the zeolite framework, the coordination of iron with 6MR is preserved despite the formation of a bond with the hydroxyl radical.

KW - цеолиты

KW - теория функционала плотности

KW - Density functional theory (DFT)

KW - MOR zeolite

KW - Magnetic properties

KW - α-Fe

UR - https://www.mendeley.com/catalogue/7b8d20cf-c1fa-3f50-837b-1857c56a4874/

U2 - 10.1016/j.mtcomm.2024.110418

DO - 10.1016/j.mtcomm.2024.110418

M3 - Article

VL - 41

JO - Materials Today Communications

JF - Materials Today Communications

SN - 2352-4928

M1 - 110418

ER -