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Spectroscopic definition of the copper active sites in mordenite: selective methane oxidation

Vanelderen, Pieter and Snyder, Benjamin E. R. and Tsai, Ming-Li and Hadt, Ryan G. and Vancauwenbergh, Julie and Coussens, Olivier and Schoonheydt, Robert A. and Sels, Bert F. and Solomon, Edward I. (2015) Spectroscopic definition of the copper active sites in mordenite: selective methane oxidation. Journal of the American Chemical Society, 137 (19). pp. 6383-6392. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20180612-144351445

[img] PDF (UV–vis-NIR and resonance Raman spectra of Cu-MOR after N2O activation, kinetics of the 22000 cm–1 absorption band during reaction met methane and additional Cu-MOR structures) - Supplemental Material
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Abstract

Two distinct [Cu-O-Cu]^(2+) sites with methane monooxygenase activity are identified in the zeolite Cu-MOR, emphasizing that this Cu-O-Cu active site geometry, having a ∠Cu-O-Cu ∼140°, is particularly formed and stabilized in zeolite topologies. Whereas in ZSM-5 a similar [Cu-O-Cu]^(2+) active site is located in the intersection of the two 10 membered rings, Cu-MOR provides two distinct local structures, situated in the 8 membered ring windows of the side pockets. Despite their structural similarity, as ascertained by electronic absorption and resonance Raman spectroscopy, the two Cu-O-Cu active sites in Cu-MOR clearly show different kinetic behaviors in selective methane oxidation. This difference in reactivity is too large to be ascribed to subtle differences in the ground states of the Cu-O-Cu sites, indicating the zeolite lattice tunes their reactivity through second-sphere effects. The MOR lattice is therefore functionally analogous to the active site pocket of a metalloenzyme, demonstrating that both the active site and its framework environment contribute to and direct reactivity in transition metal ion-zeolites.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/jacs.5b02817DOIArticle
https://pubs.acs.org/doi/suppl/10.1021/jacs.5b02817PublisherSupporting Information
ORCID:
AuthorORCID
Hadt, Ryan G.0000-0001-6026-1358
Solomon, Edward I.0000-0003-0291-3199
Additional Information:© 2015 American Chemical Society. Received: March 17, 2015. Published: April 26, 2015. P.V. acknowledges KU Leuven for a postdoctoral fellowship and the FWO for a travel grant during his stay at Stanford University. B.E.R.S. acknowledges support from the National Science Foundation Graduate Research Fellowship Program under Grant No. DGE-11474, and from the Munger, Pollock, Reynolds, Robinson, Smith & Yoedicke Stanford Graduate Fellowship. This work was supported by National Science Foundation Grants CHE-1360046 (to E.I.S.) and funded within the framework of FWO (G.0596.11), M.-L.T. received support from the Postdoctoral Research Abroad Program sponsored by the National Science Council, Taiwan (R.O.C.) and R.G.H. acknowledges a Gerhard Casper Stanford Graduate Fellowship and the Achievement Rewards for College Scientists (ARCS) Foundation. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
Katholieke Universiteit LeuvenUNSPECIFIED
Fonds Wetenschappelijk Onderzoek (FWO)G.0596.11
NSF Graduate Research FellowshipDGE-114747
Stanford UniversityUNSPECIFIED
NSFCHE-1360046
National Science Council (Taipei)UNSPECIFIED
ARCS FoundationUNSPECIFIED
Issue or Number:19
Record Number:CaltechAUTHORS:20180612-144351445
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180612-144351445
Official Citation:Spectroscopic Definition of the Copper Active Sites in Mordenite: Selective Methane Oxidation Pieter Vanelderen, Benjamin E. R. Snyder, Ming-Li Tsai, Ryan G. Hadt, Julie Vancauwenbergh, Olivier Coussens, Robert A. Schoonheydt, Bert F. Sels, and Edward I. Solomon Journal of the American Chemical Society 2015 137 (19), 6383-6392 DOI: 10.1021/jacs.5b02817
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:87026
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:12 Jun 2018 22:02
Last Modified:03 Oct 2019 19:51

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