Please use this identifier to cite or link to this item: https://doi.org/10.1038/nature19059
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dc.titleThe active site of low-temperature methane hydroxylation in iron-containing zeolites
dc.contributor.authorSnyder, Benjamin ER
dc.contributor.authorVanelderen, Pieter
dc.contributor.authorBols, Max L
dc.contributor.authorHallaert, Simon D
dc.contributor.authorBottger, Lars H
dc.contributor.authorUngur, Liviu
dc.contributor.authorPierloot, Kristine
dc.contributor.authorSchoonheydt, Robert A
dc.contributor.authorSels, Bert F
dc.contributor.authorSolomon, Edward I
dc.date.accessioned2022-07-18T15:02:29Z
dc.date.available2022-07-18T15:02:29Z
dc.date.issued2016-08-18
dc.identifier.citationSnyder, Benjamin ER, Vanelderen, Pieter, Bols, Max L, Hallaert, Simon D, Bottger, Lars H, Ungur, Liviu, Pierloot, Kristine, Schoonheydt, Robert A, Sels, Bert F, Solomon, Edward I (2016-08-18). The active site of low-temperature methane hydroxylation in iron-containing zeolites. NATURE 536 (7616) : 317-+. ScholarBank@NUS Repository. https://doi.org/10.1038/nature19059
dc.identifier.issn0028-0836
dc.identifier.issn1476-4687
dc.identifier.urihttps://scholarbank.nus.edu.sg/handle/10635/228794
dc.description.abstractAn efficient catalytic process for converting methane into methanol could have far-reaching economic implications. Iron-containing zeolites (microporous aluminosilicate minerals) are noteworthy in this regard, having an outstanding ability to hydroxylate methane rapidly at room temperature to form methanol. Reactivity occurs at an extra-lattice active site called α-Fe(ii), which is activated by nitrous oxide to form the reactive intermediate α-O; however, despite nearly three decades of research, the nature of the active site and the factors determining its exceptional reactivity are unclear. The main difficulty is that the reactive species - α-Fe(ii) and α-O - are challenging to probe spectroscopically: data from bulk techniques such as X-ray absorption spectroscopy and magnetic susceptibility are complicated by contributions from inactive ' spectator' iron. Here we show that a site-selective spectroscopic method regularly used in bioinorganic chemistry can overcome this problem. Magnetic circular dichroism reveals α-Fe(ii) to be a mononuclear, high-spin, square planar Fe(ii) site, while the reactive intermediate, α-O, is a mononuclear, high-spin Fe(iv)=O species, whose exceptional reactivity derives from a constrained coordination geometry enforced by the zeolite lattice. These findings illustrate the value of our approach to exploring active sites in heterogeneous systems. The results also suggest that using matrix constraints to activate metal sites for function - producing what is known in the context of metalloenzymes as an ' entatic' state - might be a useful way to tune the activity of heterogeneous catalysts.
dc.language.isoen
dc.publisherNATURE PUBLISHING GROUP
dc.sourceElements
dc.subjectScience & Technology
dc.subjectMultidisciplinary Sciences
dc.subjectScience & Technology - Other Topics
dc.subjectCIRCULAR-DICHROISM SPECTROSCOPY
dc.subjectDENSITY-FUNCTIONAL THEORY
dc.subjectELECTRONIC-STRUCTURE
dc.subjectPERTURBATION-THEORY
dc.subjectFEZSM-5 ZEOLITE
dc.subjectFE-BEA
dc.subjectCATALYSTS
dc.subjectENZYMES
dc.subjectCOMPLEXES
dc.subjectOXIDATION
dc.typeArticle
dc.date.updated2022-07-15T02:42:25Z
dc.contributor.departmentDEPT OF CHEMISTRY
dc.description.doi10.1038/nature19059
dc.description.sourcetitleNATURE
dc.description.volume536
dc.description.issue7616
dc.description.page317-+
dc.published.statePublished
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