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Cu<jats:sup>+<\/jats:sup>\/Cu<jats:sup>0<\/jats:sup> site is beneficial for C\u2212C coupling process, but the oxidation state of copper cannot be well maintained during the reaction process, resulting in a decrease in catalyst activity. Based on this consideration, in this work, transition metal oxide CeO<jats:sub>2<\/jats:sub> with a hollow cube structure and oxygen vacancies was introduced to stabilize and increase Cu<jats:sup>+<\/jats:sup>\/Cu<jats:sup>0<\/jats:sup> active sites (Ce<jats:sub>1<\/jats:sub>Cu<jats:sub>2<\/jats:sub>). The catalyst exhibits excellent CO<jats:sub>2<\/jats:sub>RR performance, with FE<jats:sub>C2+<\/jats:sub> achieving 73.52\u2009% and j<jats:sub>C2+<\/jats:sub> &gt;280\u2005mA\/cm<jats:sup>2<\/jats:sup> at 1.26\u2005V (vs. RHE). Ethanol is the main C<jats:sub>2+<\/jats:sub> product and FE<jats:sub>ethanol<\/jats:sub> reaches 39\u2009% at 1.26\u2005V. The experimental results indicate that the presence of CeO<jats:sub>2<\/jats:sub> provides a large number of oxygen vacancies and forming Cu<jats:sup>+<\/jats:sup>\u2010O<jats:sup>2\u2212<\/jats:sup>\u2010Ce<jats:sup>4+<\/jats:sup> structure by the strong interaction of CeO<jats:sub>2<\/jats:sub> and Cu NPs. The structure of Cu<jats:sup>+<\/jats:sup>\u2010O<jats:sup>2\u2212<\/jats:sup>\u2010Ce<jats:sup>4+<\/jats:sup> and abundant oxygen vacancies lay a good foundation for the CO<jats:sub>2<\/jats:sub> adsorption. Moreover, it increases the content of Cu<jats:sup>+<\/jats:sup>\/Cu<jats:sup>0<\/jats:sup> sites, effectively inhibiting hydrogen evolution reaction, promoting the C\u2212C coupling interaction, thereby facilitating the generation of C<jats:sub>2+<\/jats:sub> products. The DFT theoretical calculation further demonstrates that Ce<jats:sub>1<\/jats:sub>Cu<jats:sub>2<\/jats:sub> is more inclined towards the ethanol pathway, confirming its high selectivity for ethanol.<\/jats:p>","DOI":"10.1002\/cssc.202402097","type":"journal-article","created":{"date-parts":[[2024,11,18]],"date-time":"2024-11-18T22:53:36Z","timestamp":1731970416000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":7,"title":["Cerium Dioxide\u2010Induced Abundant Cu<sup>+<\/sup>\/Cu<sup>0<\/sup> Sites for Electrocatalytic Reduction of Carbon Dioxide to C<sub>2+<\/sub> Products"],"prefix":"10.1002","volume":"18","author":[{"given":"Yuwen","family":"Wang","sequence":"first","affiliation":[{"name":"Academy of Interdisciplinary Studies on Intelligent Molecules Tianjin Key Laboratory of Structure and Performance for Functional Molecules College of Chemistry Tianjin Normal University  Tianjin 300387 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