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Ag\u2010Bi<jats:sub>2<\/jats:sub>O<jats:sub>3<\/jats:sub> selectively reduces gaseous CO<jats:sub>2<\/jats:sub> to formate at neutral pH conditions. A subsequent enzymatic cascade comprising formaldehyde dehydrogenase and alcohol dehydrogenase, which are both nicotinamide adenine dinucleotide (NAD)\u2010dependent, further reduce formate sequentially to formaldehyde and methanol. The enzymatically oxidized redox cofactor NAD<jats:sup>+<\/jats:sup> is regenerated through the enzyme diaphorase which is electrochemically coupled to the electrode by embedding it into a cobaltocene\u2010based low\u2010potential redox polymer. Methanol formation is confirmed using a highly selective biosensor based on alcohol oxidase in combination with horseradish peroxidase integrated into a specifically adapted redox polymer. The proposed hybrid electrocatalytic\u2010bioelectrocatalytic cascade is an example for a general strategy for enhancing the selectivity of electrocatalytic reactions and\/or to replace bioelectrochemically challenging steps such as the synthesis of formate from CO<jats:sub>2<\/jats:sub> using highly oxygen\u2010sensitive formate dehydrogenases by more robust inorganic electrocatalysts.<\/jats:p>","DOI":"10.1002\/anie.202422882","type":"journal-article","created":{"date-parts":[[2024,12,23]],"date-time":"2024-12-23T15:59:20Z","timestamp":1734969560000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":20,"title":["Hybrid Enzyme\u2010Electrocatalyst Cascade Modified Gas\u2010Diffusion Electrodes for Methanol Formation from Carbon 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