Is [FeO]2+ the Active Center Also in Iron Containing Zeolites? A Density Functional Theory Study of Methane Hydroxylation Catalysis by Fe-ZSM-5 Zeolite

被引：55

作者：

Rosa, Angela ^{[1
]}

Ricciardi, Giampaolo ^{[1
]}

Baerends, Evert Jan ^{[2
,3
]}

机构：

[1] Univ Basilica, Dipartimento Chim, I-85100 Potenza, Italy

[2] Pohang Univ Sci & Technol, Dept Chem, Pohang 790784, South Korea

[3] Vrije Univ Amsterdam, NL-1081 HV Amsterdam, Netherlands

来源：

INORGANIC CHEMISTRY | 2010年 / 49卷 / 08期

关键词：

MULTIREFERENCE AB-INITIO; SPIN FE(IV) COMPLEX; HIGH-VALENT IRON; ELECTRONIC-STRUCTURE; PHENOL OXIDATION; FE-IV=O; SPECTROSCOPIC CHARACTERIZATION; KETOGLUTARATE DIOXYGENASE; BIOMIMETIC OXIDATION; 2-STATE REACTIVITY;

D O I：

10.1021/ic1000073

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Arguments are put forward that the active a-oxygen site in the Fe-ZSM-5 catalyst consists of the FeO2+ moiety. It is demonstrated that this zeolite site for FeO2+ indeed obeys the design principles for high reactivity of the FeO2+ moiety proposed earlier: a ligand environment consisting of weak equatorial donors (rather oxygen based than nitrogen based) and very weak or absent trans axial donor. The alpha-oxygen site would then owe its high reactivity to the same electronic structure features that lends FeO2+ its high activity in biological systems, as well as in the classical Fenton chemistry.

引用

页码：3866 / 3880

页数：15

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