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Inspired by the monocopper active site of methane monooxygenase, we synthesized a Cu-doped ZIF-8 metal\u2013organic framework with 25% Cu and 75% Zn in the nodes and activated it by heating to 200 \u00b0C and dosing in a stepwise fashion with O2, methane, and steam. We found that it does oxidize methane to methanol and formaldehyde. The catalysis persists through at least five cycles, and beyond the third cycle, the selectivity improves to the extent that no CO2 can be detected. Experimental characterization and analysis were carried out by PXRD, DRUV\u2212vis, SEM, and XAS (XANES and EXAFS). The reaction is postulated to proceed at open-coordination copper sites generated by defects, and the mechanism of methanol production was explicated by density functional calculations with the revMO6-L exchange\u2013correlation functional. The calculations reveal a catalytic cycle of oxygen-activated CuI involving the conversion of two molecules of CH4 to two molecules of CH3OH by a sequence of hydrogen atom transfer reactions and rebound steps. For most steps in the cycle, the reaction is more favored by singlet species than by triplets.<\/jats:p>","DOI":"10.1021\/jacs.3c06981","type":"journal-article","created":{"date-parts":[[2023,10,2]],"date-time":"2023-10-02T10:24:28Z","timestamp":1696242268000},"page":"22019-22030","source":"Crossref","is-referenced-by-count":37,"title":["Bioinspired Cu(II)\nDefect Sites in ZIF\u20118 for\nSelective Methane Oxidation"],"prefix":"10.1021","volume":"145","author":[{"given":"Ying","family":"Yang","sequence":"first","affiliation":[{"name":"Northwestern University , , , ,","place":["Evanston, Illinois, United States, 60208"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4906-020X","authenticated-orcid":true,"given":"Siriluk","family":"Kanchanakungwankul","sequence":"additional","affiliation":[{"name":"University of Minnesota , , , ,","place":["Minneapolis, Minnesota, United\nStates, 55455-0431"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9568-0656","authenticated-orcid":true,"given":"Suman","family":"Bhaumik","sequence":"additional","affiliation":[{"name":"University of Minnesota , , , ,","place":["Minneapolis, Minnesota, United\nStates, 55455-0431"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6530-9322","authenticated-orcid":true,"given":"Qing","family":"Ma","sequence":"additional","affiliation":[{"name":"DND-CAT, Northwestern Synchrotron Research Center at the Advanced Photon Source , , ,","place":["Argonne, Illinois, United States, 60439"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2792-816X","authenticated-orcid":true,"given":"Sol","family":"Ahn","sequence":"additional","affiliation":[{"name":"Chung-Ang University , , 84 Heukseok-ro, Dongjak-gu , ,","place":["Seoul, Republic of Korea, 06974"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7742-7294","authenticated-orcid":true,"given":"Donald G.","family":"Truhlar","sequence":"additional","affiliation":[{"name":"University of Minnesota , , , ,","place":["Minneapolis, Minnesota, United\nStates, 55455-0431"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3982-9812","authenticated-orcid":true,"given":"Joseph T.","family":"Hupp","sequence":"additional","affiliation":[{"name":"Northwestern University , , , ,","place":["Evanston, Illinois, United States, 60208"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2023,10,2]]},"reference":[{"key":"2026081707183453200_cit1","doi-asserted-by":"publisher","first-page":"49","DOI":"10.1016\/j.apenergy.2015.03.040","article-title":"A Review of the Technical and Economic Evaluation Techniques\nfor Shale Gas Development","volume":"148","author":"Yuan","year":"2015","journal-title":"Appl. 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Technol."},{"key":"2026081707183453200_cit41","doi-asserted-by":"publisher","first-page":"10186","DOI":"10.1073\/pnas.0602439103","article-title":"Exceptional Chemical and Thermal Stability of Zeolitic\nImidazolate Frameworks","volume":"103","author":"Park","year":"2006","journal-title":"Proc. Natl. Acad. Sci.\nU.S.A."},{"key":"2026081707183453200_cit42","doi-asserted-by":"publisher","first-page":"1557","DOI":"10.1002\/anie.200503778","article-title":"Ligand-Directed\nStrategy for Zeolite-Type Metal\u2013Organic Frameworks: Zinc\u00ad(II)\nImidazolates with Unusual Zeolitic Topologies","volume":"45","author":"Huang","year":"2006","journal-title":"Angew. Chem., Int. 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A"},{"key":"2026081707183453200_cit47","doi-asserted-by":"publisher","first-page":"16562","DOI":"10.1039\/C9DT03181B","article-title":"Coexistence\nof Cu\u00ad(II) and Cu\u00ad(I) in Cu Ion-Doped Zeolitic Imidazolate Frameworks\n(ZIF-8) for the Dehydrogenative Coupling of Silanes with Alcohols","volume":"48","author":"Dai","year":"2019","journal-title":"Dalton Trans."},{"key":"2026081707183453200_cit48","doi-asserted-by":"publisher","first-page":"12653","DOI":"10.1039\/C6DT01827K","article-title":"Unveiling\nthe Adsorption Mechanism of Zeolitic Imidazolate Framework-8 with\nHigh Efficiency for Removal of Copper Ions from Aqueous Solutions","volume":"45","author":"Zhang","year":"2016","journal-title":"Dalton Trans."},{"key":"2026081707183453200_cit49","doi-asserted-by":"publisher","first-page":"6670","DOI":"10.1039\/D0SC01397H","article-title":"Thermally Treated Zeolitic Imidazolate Framework-8 (ZIF-8) for Visible\nLight Photocatalytic Degradation of Gaseous Formaldehyde","volume":"11","author":"Wang","year":"2020","journal-title":"Chem. 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