{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,16]],"date-time":"2026-09-16T08:58:33Z","timestamp":1789549113000,"version":"build-2803163510"},"reference-count":59,"publisher":"Wiley","issue":"23","license":[{"start":{"date-parts":[[2024,4,30]],"date-time":"2024-04-30T00:00:00Z","timestamp":1714435200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by-nc-nd\/4.0\/"}],"funder":[{"DOI":"10.13039\/100000086","name":"Directorate for Mathematical and Physical Sciences","doi-asserted-by":"publisher","award":["CHE-1800284"],"award-info":[{"award-number":["CHE-1800284"]}],"id":[{"id":"10.13039\/100000086","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2024,6,3]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>\n                    In the past, Cu\u2010oxo or \u2010hydroxy clusters hosted in zeolites have been suggested to enable the selective conversion of methane to methanol, but the impact of the active site's stoichiometry and structure on methanol production is still poorly understood. Herein, we apply theoretical modeling in conjunction with experiments to study the impact of these two factors on partial methane oxidation in the Cu\u2010exchanged zeolite SSZ\u201013. Phase diagrams developed from first\u2010principles suggest that Cu\u2010hydroxy or Cu\u2010oxo dimers are stabilized when O\n                    <jats:sub>2<\/jats:sub>\n                    or N\n                    <jats:sub>2<\/jats:sub>\n                    O are used to activate the catalyst, respectively. We confirm these predictions experimentally and determine that in a stepwise conversion process, Cu\u2010oxo dimers can convert twice as much methane to methanol compared to Cu\u2010hydroxyl dimers. Our theoretical models rationalize how Cu\u2010di\u2010oxo dimers can convert up to two methane molecules to methanol, while Cu\u2010di\u2010hydroxyl dimers can convert only one methane molecule to methanol per catalytic cycle. These findings imply that in Cu clusters, at least one oxo group or two hydroxyl groups are needed to convert one methane molecule to methanol per cycle. This simple structure\u2013activity relationship allows to intuitively understand the potential of small oxygenated or hydroxylated transition metal clusters to convert methane to methanol.\n                  <\/jats:p>","DOI":"10.1002\/anie.202403179","type":"journal-article","created":{"date-parts":[[2024,4,4]],"date-time":"2024-04-04T15:59:19Z","timestamp":1712246359000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":27,"title":["Exploring the Impact of Active Site Structure on the Conversion of Methane to Methanol in Cu\u2010Exchanged Zeolites"],"prefix":"10.1002","volume":"63","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-7217-0450","authenticated-orcid":false,"given":"Florian","family":"G\u00f6ltl","sequence":"first","affiliation":[{"name":"The University of Arizona Department of Biosystems Engineering  1177, E 4th St. 85719 Tucson AZ United States"},{"name":"The University of Wisconsin \u2013 Madison Department of Chemical and Biological Engineering  1415 Engineering Drive 53706 Madison WI United States"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Saurabh","family":"Bhandari","sequence":"additional","affiliation":[{"name":"The University of Wisconsin \u2013 Madison Department of Chemical and Biological Engineering  1415 Engineering Drive 53706 Madison WI United States"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Edgard A.","family":"Lebr\u00f3n\u2010Rodr\u00edguez","sequence":"additional","affiliation":[{"name":"The University of Wisconsin \u2013 Madison Department of Chemical and Biological Engineering  1415 Engineering Drive 53706 Madison WI United States"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jake I.","family":"Gold","sequence":"additional","affiliation":[{"name":"The University of Wisconsin \u2013 Madison Department of Chemical and Biological Engineering  1415 Engineering Drive 53706 Madison WI United States"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Daniel J.","family":"Hutton","sequence":"additional","affiliation":[{"name":"The University of Arizona Department of Biosystems Engineering  1177, E 4th St. 85719 Tucson AZ United States"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Stacey I.","family":"Zones","sequence":"additional","affiliation":[{"name":"Chevron Energy Technology Company  Richmond CA 94804 United States"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ive","family":"Hermans","sequence":"additional","affiliation":[{"name":"The University of Wisconsin \u2013 Madison Department of Chemical and Biological Engineering  1415 Engineering Drive 53706 Madison WI United States"},{"name":"The University of Wisconsin \u2013 Madison Department of Chemistry 1101 University Avenue  53706 Madison WI United States"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"James A.","family":"Dumesic","sequence":"additional","affiliation":[{"name":"The University of Wisconsin \u2013 Madison Department of Chemical and Biological Engineering  1415 Engineering Drive 53706 Madison WI United States"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Manos","family":"Mavrikakis","sequence":"additional","affiliation":[{"name":"The University of Wisconsin \u2013 Madison Department of Chemical and Biological Engineering  1415 Engineering Drive 53706 Madison WI United States"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2024,4,30]]},"reference":[{"key":"e_1_2_7_1_1","doi-asserted-by":"publisher","DOI":"10.1039\/C4CY00327F"},{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1039\/C6CS00324A"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/cs200055d"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.8b00220"},{"key":"e_1_2_7_5_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41929-019-0273-z"},{"key":"e_1_2_7_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.8b01180"},{"key":"e_1_2_7_7_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2012.07.008"},{"key":"e_1_2_7_8_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.7b00344"},{"key":"e_1_2_7_9_1","doi-asserted-by":"publisher","DOI":"10.1038\/nmat4760"},{"issue":"7616","key":"e_1_2_7_10_1","first-page":"317","volume":"536","author":"Snyder B. 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