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Although UiO\u201066\u2010based composites containing Cu and Cu\u2010Zn species show promising performance for CO\n                    <jats:sub>2<\/jats:sub>\n                    \u2010to\u2010methanol conversion, the role of the MOF framework in stabilizing the active metallic species under working conditions remains insufficiently understood. Here, the stabilization of copper species by UiO\u201066 and the influence of Zn promotion on Cu speciation and catalytic performance during CO\n                    <jats:sub>2<\/jats:sub>\n                    hydrogenation are investigated. Operando X\u2010ray absorption spectroscopy at the Cu, Zn, and Zr K\u2010edges is combined with electron microscopy and density functional theory calculations to follow the evolution of metal species and the framework during reduction, reaction, and transient switching experiments. Zn promotes the formation and stability of highly dispersed Cu under reaction conditions, while the Zr\n                    <jats:sub>6<\/jats:sub>\n                    nodes of UiO\u201066 respond dynamically through reversible hydroxylation and dehydroxylation. By correlating metal speciation, framework response, and methanol productivity under continuous\u2010flow conditions, this work provides molecular\u2010level insight into metal stabilization in Zr\u2010based MOFs and informs the design of MOF\u2010based catalysts for CO\n                    <jats:sub>2<\/jats:sub>\n                    hydrogenation.\n                  <\/jats:p>","DOI":"10.1002\/smll.74210","type":"journal-article","created":{"date-parts":[[2026,7,1]],"date-time":"2026-07-01T16:30:43Z","timestamp":1782923443000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Stabilization of Cu Species in UiO\u201066 Metal\u2013Organic Framework for CO\n                    <sub>2<\/sub>\n                    \u2010to\u2010Methanol: Insights From Operando X\u2010ray and Electron Microscopy Studies"],"prefix":"10.1002","volume":"22","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-8826-7532","authenticated-orcid":false,"given":"Anna","family":"Liutkova","sequence":"first","affiliation":[{"name":"Center for Energy and Environmental Sciences PSI  Villigen Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5036-1475","authenticated-orcid":false,"given":"Fabio Andr\u00e9","family":"Peixoto Esteves","sequence":"additional","affiliation":[{"name":"Center for Energy and Environmental Sciences PSI  Villigen Switzerland"},{"name":"Department of Chemistry and Applied Biosciences ETH Z\u00fcrich  Zurich Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0002-9723-8252","authenticated-orcid":false,"given":"Marianela","family":"L\u00f3pez Romero","sequence":"additional","affiliation":[{"name":"Center for Energy and Environmental Sciences PSI  Villigen 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