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Both methanol and ethanol are versatile chemical feedstock and renewable fuels. The ionic hybrid compound [Zr<jats:sub>6<\/jats:sub>O<jats:sub>4<\/jats:sub>(OH)<jats:sub>4<\/jats:sub>(C<jats:sub>6<\/jats:sub>H<jats:sub>5<\/jats:sub>COO)<jats:sub>8<\/jats:sub>(H<jats:sub>2<\/jats:sub>O)<jats:sub>8<\/jats:sub>][SiW<jats:sub>12<\/jats:sub>O<jats:sub>40<\/jats:sub>] (<jats:bold>Zr<jats:sub>6<\/jats:sub>W<jats:sub>12<\/jats:sub><\/jats:bold>) provides effective separation of the generated electron\u2010hole pair during exposure to UV radiation through a Z\u2010scheme disposition of the HOMO\u2010LUMO levels of each discrete ionic entity. However, this compound does not promote the CO<jats:sub>2<\/jats:sub> reduction. In contrast, the incorporation of selected inorganic cocatalysts, such as AgI, Bi<jats:sub>2<\/jats:sub>O<jats:sub>3<\/jats:sub>, CeO<jats:sub>2<\/jats:sub>, CuI, CuO, Cu<jats:sub>2<\/jats:sub>O, In<jats:sub>2<\/jats:sub>O<jats:sub>3<\/jats:sub>, PbO, Sb<jats:sub>2<\/jats:sub>O<jats:sub>3<\/jats:sub>, SnO, TiO<jats:sub>2<\/jats:sub> or ZnO, to the photocatalytic system can enable the activation and reduction of CO<jats:sub>2<\/jats:sub>, leveraging their electronic properties and interactions with <jats:bold>Zr<jats:sub>6<\/jats:sub>W<jats:sub>12<\/jats:sub><\/jats:bold>. Some of these heterogeneous photocatalytic systems perform well for the photoreduction of CO<jats:sub>2<\/jats:sub> into methanol and\/or ethanol in water and without the need of any sacrificial chemical reagent, achieving maximum production levels of 163\u2005\u03bcg\u2009g<jats:sup>\u22121<\/jats:sup>\u2009h<jats:sup>\u22121<\/jats:sup> and 144\u2005\u03bcg\u2009g<jats:sup>\u22121<\/jats:sup>\u2009h<jats:sup>\u22121<\/jats:sup> for methanol and ethanol, respectively, for the Zr<jats:sub>6<\/jats:sub>W<jats:sub>12<\/jats:sub>\/CuI photocatalytic mixture. Theoretical calculations have been conducted to determine how the relative disposition of the HOMO\/LUMO energy levels of <jats:bold>Zr<jats:sub>6<\/jats:sub>W<jats:sub>12<\/jats:sub><\/jats:bold> and the band structure of the inorganic cocatalysts impact on the CO<jats:sub>2<\/jats:sub> photocatalytic reduction to alcohols.<\/jats:p>","DOI":"10.1002\/cssc.202402694","type":"journal-article","created":{"date-parts":[[2025,3,20]],"date-time":"2025-03-20T14:44:27Z","timestamp":1742481867000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Heterogeneous Photocatalytic Systems Formed by Compound [Zr<sub>6<\/sub>O<sub>4<\/sub>(OH)<sub>4<\/sub>(C<sub>6<\/sub>H<sub>5<\/sub>COO)<sub>8<\/sub>(H<sub>2<\/sub>O)<sub>8<\/sub>][SiW<sub>12<\/sub>O<sub>40<\/sub>] in Combination with Inorganic Cocatalysts for the CO<sub>2<\/sub> Reduction to Alcohols in Water"],"prefix":"10.1002","volume":"18","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-8895-6677","authenticated-orcid":false,"given":"Jon","family":"Napal","sequence":"first","affiliation":[{"name":"Department of Organic and Inorganic Chemistry University of the Basque Country, UPV\/EHU  P.O. 644 E-48080 Bilbao Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0009-0006-0202-9503","authenticated-orcid":false,"given":"Raquel","family":"L\u00f3pez","sequence":"additional","affiliation":[{"name":"Department of Organic and Inorganic Chemistry University of the Basque Country, UPV\/EHU  P.O. 644 E-48080 Bilbao Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2751-5592","authenticated-orcid":false,"given":"Fernando","family":"Aguilar\u2010Galindo","sequence":"additional","affiliation":[{"name":"Department of Chemistry Autonomous University of Madrid, UAM  28049 Madrid Spain"},{"name":"Institute for Advanced Research in Chemical Sciences (IAdChem) Autonomous University of Madrid, UAM  28049 Madrid Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7373-4596","authenticated-orcid":false,"given":"Be\u00f1at","family":"Artetxe","sequence":"additional","affiliation":[{"name":"Department of Organic and Inorganic Chemistry University of the Basque Country, UPV\/EHU  P.O. 644 E-48080 Bilbao Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6262-6506","authenticated-orcid":false,"given":"Garikoitz","family":"Beobide","sequence":"additional","affiliation":[{"name":"Department of Organic and Inorganic Chemistry University of the Basque Country, UPV\/EHU  P.O. 644 E-48080 Bilbao Spain"},{"name":"BCMaterials, Basque Center for Materials Applications and Nanostructures  E-48940 Leioa Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5614-9301","authenticated-orcid":false,"given":"Oscar","family":"Castillo","sequence":"additional","affiliation":[{"name":"Department of Organic and Inorganic Chemistry University of the Basque Country, UPV\/EHU  P.O. 644 E-48080 Bilbao Spain"},{"name":"BCMaterials, Basque Center for Materials Applications and Nanostructures  E-48940 Leioa Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8827-0384","authenticated-orcid":false,"given":"Antonio","family":"Luque","sequence":"additional","affiliation":[{"name":"Department of Organic and Inorganic Chemistry University of the Basque Country, UPV\/EHU  P.O. 644 E-48080 Bilbao Spain"},{"name":"BCMaterials, Basque Center for Materials Applications and Nanostructures  E-48940 Leioa Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3342-892X","authenticated-orcid":false,"given":"Sonia","family":"P\u00e9rez\u2010Y\u00e1\u00f1ez","sequence":"additional","affiliation":[{"name":"BCMaterials, Basque Center for Materials Applications and Nanostructures  E-48940 Leioa Spain"},{"name":"Department of Organic and Inorganic Chemistry University of the Basque Country, UPV\/EHU  E-01006 Vitoria-Gasteiz Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2025,5,6]]},"reference":[{"key":"e_1_2_10_1_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.matpr.2023.07.147"},{"key":"e_1_2_10_2_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-021-22839-0"},{"key":"e_1_2_10_3_1","first-page":"181","volume":"106","author":"MacFarlane J. 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