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The underlying structure\u2013reactivity correlation and reaction mechanism desperately demand elucidation. Here we report the first in situ X\u2010ray absorption spectroscopy characterization, combined with ex situ spectroscopic and electrocatalytic measurements, to study CoPc\u2010catalyzed CO<jats:sub>2<\/jats:sub> reduction to methanol. Molecular dispersion of CoPc on CNT surfaces, as evidenced by the observed electronic interaction between the two, is crucial to fast electron transfer to the active sites and multi\u2010electron CO<jats:sub>2<\/jats:sub> reduction. CO, the key intermediate in the CO<jats:sub>2<\/jats:sub>\u2010to\u2010methanol pathway, is found to be labile on the active site, which necessitates a high local concentration in the microenvironment to compete with CO<jats:sub>2<\/jats:sub> for active sites and promote methanol production. A comparison of the electrocatalytic performance of structurally related porphyrins indicates that the bridging aza\u2010N atoms of the Pc macrocycle are critical components of the CoPc active site that produces methanol. In situ X\u2010ray absorption spectroscopy identifies the active site as Co(I) and supports an increasingly non\u2010centrosymmetric Co coordination environment at negative applied potential, likely due to the formation of a Co\u2212CO adduct during the catalysis.<\/jats:p>","DOI":"10.1002\/anie.202310623","type":"journal-article","created":{"date-parts":[[2023,10,11]],"date-time":"2023-10-11T19:20:32Z","timestamp":1697052032000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":127,"title":["Active Sites of Cobalt Phthalocyanine in Electrocatalytic CO<sub>2<\/sub> Reduction to Methanol"],"prefix":"10.1002","volume":"63","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-7058-568X","authenticated-orcid":false,"given":"Conor L.","family":"Rooney","sequence":"first","affiliation":[{"name":"Department of Chemistry Yale University  New Haven CT 06520 USA"},{"name":"Energy Sciences Institute Yale University  West Haven CT 06516 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