Entropic influence on the generation of Fe(IV)O species at mononuclear Fe(II) sites in metal-organic frameworks

Fernan Saiz; Leonardo Bernasconi

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Entropic influence on the generation of Fe(IV)O species at mononuclear Fe(II) sites in metal-organic frameworks

机译：Entropic influence on the generation of Fe(IV)O species at mononuclear Fe(II) sites in metal-organic frameworks

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We study the oxidation of mononuclear Fe(II) centers in the metal-organic framework MOF-74 in the presence of nitric oxide (NO), nitrogen dioxide (NO2), nitrous oxide (N2O), dinitrous dioxide (N2O2), oxygen (O2), ozone (O3), and hydrogen peroxide (H2O2) using static density-functional theory calculations and ab initio molecular dynamics simulations. We examine the effect of reaction entropies at room temperature on the Fe(II) oxidation barriers for these species. Singlet N2O, O2 and H2O2 exhibit large positive entropic contributions, which reduce the free energy barrier at room temperature compared to the enthalpy barriers. By contrast, large negative entropies are observed in the case of NO2 and O3, which indicate that the reactivity of these species decreases with temperature. We discuss the role of entropic effects on the mechanisms and energetics of the reactions examined.

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《Catalysis science & technology》 |2023年第19期|5689-5701|共13页
作者
Fernan Saiz; Leonardo Bernasconi;
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ALBA Synchrotron, Carrer de la Llum 2-26, Cerdanyola del Valles 08290, Spain;

Center for Research Computing and Department of Chemistry, University of Pittsburgh, 312 Schenley Place, 4420 Bayard Street, Pittsburgh, PA 15260, USA;

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中图分类物理化学（理论化学）、化学物理学;
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Entropic influence on the generation of Fe(IV)O species at mononuclear Fe(II) sites in metal-organic frameworks

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