{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,4]],"date-time":"2026-09-04T04:40:36Z","timestamp":1788496836373,"version":"build-2803163510"},"reference-count":104,"publisher":"Wiley","issue":"13","license":[{"start":{"date-parts":[[2025,2,14]],"date-time":"2025-02-14T00:00:00Z","timestamp":1739491200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":["advanced.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Advanced Science"],"published-print":{"date-parts":[[2025,4]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The evolution of active sites in Cu\u2010zeolites for the CH<jats:sub>4<\/jats:sub>\u2010to\u2010CH<jats:sub>3<\/jats:sub>OH conversion has been investigated during oxidative treatment in O<jats:sub>2<\/jats:sub>. Three samples with different frameworks but comparable Cu loadings and Si\/Al ratios have been prepared to assess the influence of topology on material oxidizability and the nature of the generated Cu(II) species. Complementary spectroscopic studies highlight that isomeric Cu(II) centers hosted within different topologies are characterized by distinct formation rates. In turn, the framework\u2010specific kinetics of Cu(II) site generation regulate the overall oxidation potential of the individual zeolites. Apart from the topology, the formation rate of different Cu(II) species is governed by their specific structure, with dimeric Cu(II) centers ([Cu<jats:sub>2<\/jats:sub>(\u00b5\u2010O)]<jats:sup>2+<\/jats:sup>) being generated faster than monomeric ([CuOH]<jats:sup>+<\/jats:sup>, Cu<jats:sup>2+<\/jats:sup>) ones. Elevated temperatures accelerate the evolution of Cu(II) monomers but cause [Cu<jats:sub>2<\/jats:sub>(\u00b5\u2010O)]<jats:sup>2+<\/jats:sup> to undergo autoreduction. The reversibility of this process is framework\u2010dependent. Consequently, even though two types of [Cu<jats:sub>2<\/jats:sub>(\u00b5\u2010O)]<jats:sup>2+<\/jats:sup> form at low temperatures in each material, only specific ones remain after high\u2010temperature treatment. The autoreduction of [Cu<jats:sub>2<\/jats:sub>(\u00b5\u2010O)]<jats:sup>2+<\/jats:sup> is accompanied by its transient reduction by hydrocarbon residues, originating from the preceding treatment in CH<jats:sub>4<\/jats:sub>. The oxidative decomposition of these impurities yields H<jats:sub>2<\/jats:sub>O, which adsorbs on [Cu<jats:sub>2<\/jats:sub>(\u00b5\u2010O)]<jats:sup>2+<\/jats:sup> masks their spectroscopic fingerprints, and renders them inactive.<\/jats:p>","DOI":"10.1002\/advs.202413870","type":"journal-article","created":{"date-parts":[[2025,2,14]],"date-time":"2025-02-14T08:53:06Z","timestamp":1739523186000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":7,"title":["Tracking Active Site Formation during Oxidative Activation of Copper\u2010Exchanged Zeolites for Methane\u2010to\u2010Methanol Conversion"],"prefix":"10.1002","volume":"12","author":[{"given":"Andreas","family":"Brenig","sequence":"first","affiliation":[{"name":"Institute for Chemical and Bioengineering ETH Zurich  Vladimir\u2010Prelog\u2010Weg 1\u20135\/10 Zurich 8093 Switzerland"},{"name":"Paul Scherrer Institute Center for Energy and Environmental Sciences  Forschungsstrasse 111 Villigen 5232 Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"J\u00f6rg W. 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