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In this work, we introduce a novel ZnHfO\n \n x<\/jats:sub>\n <\/jats:italic>\n catalyst that exceeds the intrinsic methanol formation rate of the reference ZnZrO\n \n x<\/jats:sub>\n <\/jats:italic>\n at a Zn content of 20 mol% (\n r<\/jats:italic>\n MeOH,20ZnZrOx<\/jats:sub>\n = 0.59 mol\n MeOH<\/jats:sub>\n (mol\n cat<\/jats:sub>\n h)\n \u22121<\/jats:sup>\n ,\n r<\/jats:italic>\n MeOH,20ZnHfOx<\/jats:sub>\n = 0.68 mol\n MeOH<\/jats:sub>\n (mol\n cat<\/jats:sub>\n h)\n \u22121<\/jats:sup>\n ). Remarkably and in contrast to ZnZrO\n \n x<\/jats:sub>\n <\/jats:italic>\n , the ZnHfO\n \n x<\/jats:sub>\n <\/jats:italic>\n \u2010based catalysts exhibit a high methanol selectivity (> 70%) up to Zn contents of 99.5 mol% despite the segregation of ZnO. Operando spectroscopy, in combination with computational analysis, identifies the Zn\u2013V\n O<\/jats:sub>\n \u2013Hf motif as the active site for methanol formation that proceeds via the formate\u2010methoxy pathway. Such active sites are not only present in solid solution\u2010type ZnHfO\n \n x<\/jats:sub>\n <\/jats:italic>\n catalysts (\u2264 35 mol% Zn), but also in the form of isolated HfO\n \n x<\/jats:sub>\n <\/jats:italic>\n clusters on segregated ZnO surfaces (for high Zn contents of > 35 mol%), explaining the high selectivity (and activity) over a wide range of Zn contents.\n <\/jats:p>","DOI":"10.1002\/anie.8850754","type":"journal-article","created":{"date-parts":[[2026,6,30]],"date-time":"2026-06-30T13:10:23Z","timestamp":1782825023000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["The Role of Zn\u2013Hf Site Proximity and Oxygen Vacancies for Methanol Formation Over ZnHfO\n \n x<\/sub>\n <\/i>\n Catalysts Under CO\n 2<\/sub>\n Hydrogenation Conditions"],"prefix":"10.1002","volume":"65","author":[{"given":"Alexander","family":"Oing","sequence":"first","affiliation":[{"name":"Department of Mechanical and Process Engineering ETH Z\u00fcrich Z\u00fcrich Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Diana","family":"Piankova","sequence":"additional","affiliation":[{"name":"Department of Mechanical and Process Engineering ETH Z\u00fcrich Z\u00fcrich Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jean C.","family":"Villa\u2010Arpi","sequence":"additional","affiliation":[{"name":"Institute of Materials Chemistry TU Wien Vienna Austria"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Muhammad Helmi","family":"Risansyauqi","sequence":"additional","affiliation":[{"name":"Institute of Materials Chemistry TU Wien Vienna Austria"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hector","family":"Prats","sequence":"additional","affiliation":[{"name":"Institute of Materials Chemistry TU Wien Vienna Austria"},{"name":"Departament De Ci\u00e8ncia de Materials i Qu\u00edmica F\u00edsica & Institut De Qu\u00edmica Te\u00f2rica i Computacional (IQTCUB) Universitat De Barcelona Barcelona Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Felix","family":"Donat","sequence":"additional","affiliation":[{"name":"Department of Mechanical and Process Engineering ETH Z\u00fcrich Z\u00fcrich Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Paula M.","family":"Abdala","sequence":"additional","affiliation":[{"name":"Department of Mechanical and Process Engineering ETH Z\u00fcrich Z\u00fcrich Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7002-1582","authenticated-orcid":false,"given":"Aleix","family":"Comas\u2010Vives","sequence":"additional","affiliation":[{"name":"Institute of Materials Chemistry TU Wien Vienna Austria"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2234-6902","authenticated-orcid":false,"given":"Christoph 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