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Tuning Cu nuclearity toward small clusters or isolated atoms is crucial for controlling product selectivity, yet very challenging. One way to achieve this is by adjusting the number of OH\/H\n                    <jats:sub>2<\/jats:sub>\n                    O pairs on Zr\n                    <jats:sub>6<\/jats:sub>\n                    nodes. While the UiO\u201066 framework allows only one anchoring pair per node, the MOF\u2010808 can host up to six defects via formate substitution, enabling much higher Cu loadings (Cu\/Zr\n                    <jats:sub>6<\/jats:sub>\n                    up to 5.2). In addition, we found that the Cu precursor influences Cu nuclearity in MOFs: CuCl\n                    <jats:sub>2<\/jats:sub>\n                    forms mainly isolated sites (Cu\n                    <jats:sub>1<\/jats:sub>\n                    ), whereas Cu(NO\n                    <jats:sub>3<\/jats:sub>\n                    )\n                    <jats:sub>2<\/jats:sub>\n                    promotes clusters (Cu\n                    <jats:sub>x<\/jats:sub>\n                    ). Cu\n                    <jats:sub>x<\/jats:sub>\n                    \/MOF catalysts were examined for CO\n                    <jats:sub>2<\/jats:sub>\n                    hydrogenation at the gas\/solid and at liquid(gas)\/solid interfaces. At the gas\/solid interface, Cu\n                    <jats:sub>x<\/jats:sub>\n                    \/MOF catalysts showed higher activity and selectivity toward methanol, with Cu\n                    <jats:sub>x<\/jats:sub>\n                    \/UiO\u201066 outperforming the Cu\n                    <jats:sub>x<\/jats:sub>\n                    \/MOF\u2010808 catalyst, while Cu\n                    <jats:sub>1<\/jats:sub>\n                    \/MOFs were barely active toward CH\n                    <jats:sub>4<\/jats:sub>\n                    and CO formation. In the liquid phase, both Cu\n                    <jats:sub>x<\/jats:sub>\n                    \/MOF catalysts were active only for methanol formation. These results, together with detailed structural characterizations using X\u2010ray absorption and diffuse reflectance FTIR spectroscopy during pretreatment and CO\n                    <jats:sub>2<\/jats:sub>\n                    reduction, electron microscopy, and a number of basic characterizations (N\n                    <jats:sub>2<\/jats:sub>\n                    adsorption, PXRD, DR\u2010UV\u2010vis, thermal analyses, and NMR spectroscopy), are discussed in relation to the structure\u2010reactivity relationships, and are supported by DFT modeling of the Cu\n                    <jats:sub>x<\/jats:sub>\n                    ensembles in both frameworks.\n                  <\/jats:p>","DOI":"10.1002\/smtd.70882","type":"journal-article","created":{"date-parts":[[2026,8,18]],"date-time":"2026-08-18T05:46:42Z","timestamp":1787032002000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Regulating Copper Nuclearity in Metal\u2013Organic Frameworks for the Hydrogenation of Carbon Dioxide"],"prefix":"10.1002","volume":"10","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-8208-3502","authenticated-orcid":false,"given":"Soufiane","family":"Bahou","sequence":"first","affiliation":[{"name":"Leibniz Institute for Catalysis (LIKAT)  Rostock Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chanokporn","family":"Kosri","sequence":"additional","affiliation":[{"name":"National Nanotechnology Center (NANOTEC) National Science and Technology Development Agency (NSTDA) Pathum Thani Thailand"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5933-5249","authenticated-orcid":false,"given":"Ashour A.","family":"Ahmed","sequence":"additional","affiliation":[{"name":"Leibniz Institute for Catalysis (LIKAT)  Rostock Germany"},{"name":"CASUS \u2010 Center for Advanced Systems Understanding Helmholtz\u2010Zentrum Dresden\u2010Rossendorf e.V. 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