Please use this identifier to cite or link to this item:
https://doi.org/10.1038/nature19059
Title: | The active site of low-temperature methane hydroxylation in iron-containing zeolites | Authors: | Snyder, 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 |
Keywords: | Science & Technology Multidisciplinary Sciences Science & Technology - Other Topics CIRCULAR-DICHROISM SPECTROSCOPY DENSITY-FUNCTIONAL THEORY ELECTRONIC-STRUCTURE PERTURBATION-THEORY FEZSM-5 ZEOLITE FE-BEA CATALYSTS ENZYMES COMPLEXES OXIDATION |
Issue Date: | 18-Aug-2016 | Publisher: | NATURE PUBLISHING GROUP | Citation: | Snyder, 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 | Abstract: | An 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. | Source Title: | NATURE | URI: | https://scholarbank.nus.edu.sg/handle/10635/228794 | ISSN: | 0028-0836 1476-4687 |
DOI: | 10.1038/nature19059 |
Appears in Collections: | Staff Publications Elements |
Show full item record
Files in This Item:
File | Description | Size | Format | Access Settings | Version | |
---|---|---|---|---|---|---|
Snyder_Nature_2016_SI.pdf | Supporting information | 374.33 kB | Adobe PDF | CLOSED | None | |
Snyder_Nature_2016.pdf | Published version | 4.59 MB | Adobe PDF | CLOSED | None |
Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.