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We demonstrate that Pd can be encapsulated within ZIF\u20108 as atomically dispersed Pd species that function as an excited\u2010state transition metal catalyst for promoting carbon\u2013carbon (C\u2212C) cross\u2010couplings at room temperature using visible light as the driving force. Furthermore, the same material can be reduced at 250\u2009\u00b0C, forming Pd metal nanoparticles encapsulated in ZIF\u20108. This catalyst shows high rates and selectivity for carbon dioxide hydrogenation to methanol under industrially relevant conditions (250\u2009\u00b0C, 50\u2005bar): 7.46\u2005mol<jats:sub>methanol<\/jats:sub>\u2009mol<jats:sub>metal<\/jats:sub><jats:sup>\u22121<\/jats:sup>\u2009h<jats:sup>\u22121<\/jats:sup> and &gt;99\u2009%. Our results demonstrate the correlations of the catalyst structure with the performances at experimental and theoretical levels.<\/jats:p>","DOI":"10.1002\/anie.202409490","type":"journal-article","created":{"date-parts":[[2024,8,10]],"date-time":"2024-08-10T06:10:13Z","timestamp":1723270213000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":8,"title":["Highly Dispersed Pd@ZIF\u20108\u2009for Photo\u2010Assisted Cross\u2010Couplings and CO<sub>2<\/sub> to Methanol: Activity and Selectivity Insights"],"prefix":"10.1002","volume":"63","author":[{"given":"Vijay K.","family":"Velisoju","sequence":"first","affiliation":[{"name":"Multiscale Reaction Engineering, KAUST Catalysis Center (KCC) King Abdullah University of Science and Technology (KAUST)  Thuwal 23955-6900 Saudi Arabia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Enrique V.","family":"Ramos\u2010Fern\u00e1ndez","sequence":"additional","affiliation":[{"name":"KAUST Catalysis Center (KCC) King Abdullah University of Science and Technology (KAUST)  Thuwal 23955-6900 Saudi Arabia"},{"name":"Laboratorio de Materiales Avanzados, Departamento de Qu\u00edmica Inorg\u00e1nica\u2014Instituto Universitario de Materiales de Alicante Universidad de Alicante  Apartado 99 E-03080 Alicante Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Rajesh","family":"Kancherla","sequence":"additional","affiliation":[{"name":"KAUST Catalysis Center (KCC) King Abdullah University of Science and Technology (KAUST)  Thuwal 23955-6900 Saudi Arabia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Rafia","family":"Ahmad","sequence":"additional","affiliation":[{"name":"KAUST Catalysis Center (KCC) King Abdullah University of Science and Technology (KAUST)  Thuwal 23955-6900 Saudi Arabia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kuntal","family":"Pal","sequence":"additional","affiliation":[{"name":"KAUST Catalysis Center (KCC) King Abdullah University of Science and Technology (KAUST)  Thuwal 23955-6900 Saudi Arabia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hend","family":"Mohamed","sequence":"additional","affiliation":[{"name":"Multiscale Reaction Engineering, KAUST Catalysis Center (KCC) King Abdullah University of Science and Technology (KAUST)  Thuwal 23955-6900 Saudi Arabia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jose L.","family":"Cerrillo","sequence":"additional","affiliation":[{"name":"KAUST Catalysis Center (KCC) King Abdullah University of Science and Technology (KAUST)  Thuwal 23955-6900 Saudi Arabia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mark J.","family":"Meijerink","sequence":"additional","affiliation":[{"name":"KAUST Catalysis Center (KCC) King Abdullah University of Science and Technology (KAUST)  Thuwal 23955-6900 Saudi Arabia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Luigi","family":"Cavallo","sequence":"additional","affiliation":[{"name":"KAUST Catalysis Center (KCC) King Abdullah University of Science and Technology (KAUST)  Thuwal 23955-6900 Saudi Arabia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Magnus","family":"Rueping","sequence":"additional","affiliation":[{"name":"KAUST Catalysis Center (KCC) King Abdullah University of Science and Technology (KAUST)  Thuwal 23955-6900 Saudi Arabia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6454-9321","authenticated-orcid":false,"given":"Pedro","family":"Casta\u00f1o","sequence":"additional","affiliation":[{"name":"Multiscale Reaction Engineering, KAUST Catalysis Center (KCC) King Abdullah University of Science and Technology (KAUST)  Thuwal 23955-6900 Saudi Arabia"},{"name":"Chemical Engineering Program, Physical Science and Engineering (PSE) Division KAUST  Thuwal 23955-6900 Saudi Arabia"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2024,10,14]]},"reference":[{"issue":"111","key":"e_1_2_7_1_1","first-page":"1","volume":"11","author":"Zhu Y.","year":"2020","journal-title":"Nat. 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