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However, most MOF\u2010based electrocatalysts require a carbonization process to overcome their potentially poor conductivity and inert catalytic activity. Here, a semiconducting trinuclear Cu(I)\u2010MOF undergone low\u2010temperature activation (CuTz\u20101\u2010300) is directly employed as an electrocatalyst for producing methanol. The CuTz\u20101\u2010300 achieves a methanol faradaic efficiency of 56.41% at the working potential of \u22120.97\u00a0V versus the reversible hydrogen electrode in 0.5\u00a0<jats:sc>m<\/jats:sc> KHCO<jats:sub>3<\/jats:sub> electrolyte. The experiments and DFT calculations imply that the generation of <jats:sup>*<\/jats:sup>COOH is the rate\u2010determining step for methanol, and <jats:sup>*<\/jats:sup>CO prefers to be further reduced instead of releasing as a CO product. Specifically, the unique CuN<jats:sub>3<\/jats:sub> is correspond to nearby BF<jats:sub>4,<\/jats:sub><jats:sup>\u2212<\/jats:sup> producing subtle synergistic electronic effects that CO<jats:sub>2<\/jats:sub> binding with a relatively strong C\u00b7\u00b7\u00b7F interaction to BF<jats:sub>4<\/jats:sub><jats:sup>\u2212<\/jats:sup> and weak C\u2500H\u00b7\u00b7\u00b7O interactions from phenyl groups to enhance the localized CO<jats:sub>2<\/jats:sub> concentration by electrostatic tension. This work demonstrates the use of ionic MOF with positive univalent Cu to improve the efficiency of electrocatalytic CO<jats:sub>2<\/jats:sub> reduction.<\/jats:p>","DOI":"10.1002\/smll.202505892","type":"journal-article","created":{"date-parts":[[2025,8,13]],"date-time":"2025-08-13T12:49:53Z","timestamp":1755089393000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["Trinuclear Cu(I) Metal\u2013Organic Framework Inspires the Activation of <sup>*<\/sup>CO<sub>2<\/sub> Via Electrostatic Tension to Boost the Electrochemical Conversion of CO<sub>2<\/sub>\u2010to\u2010Methanol"],"prefix":"10.1002","volume":"21","author":[{"ORCID":"https:\/\/orcid.org\/0009-0005-2993-0919","authenticated-orcid":false,"given":"Yangyang","family":"Zhang","sequence":"first","affiliation":[{"name":"College of Chemical Engineering Zhengzhou University  Zhengzhou 450001 P. R. 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