In this paper we first report the generation of 1-butanol from carbon dioxide (CO 2 ) on a phosphorus-rich copper cathode, based on a combination of faradaic and autonomous nonfaradaic reactions. Experimental observations via in situ surface-enhanced infrared absorption spectroscopy show depletion of the CO adsorption peak. However, the faradaic efficiency of the obtained formate and acetaldehyde intermediates led us to propose a mechanism for the formation of 1-butanol that does not include a *CO dimerization step. All compounds were confirmed by nuclear magnetic resonance spectroscopy and headspace gas chromatography−mass spectrometry. In addition, 13 CO 2 labeling experiments confirmed that the origin of each product was from dissolved CO 2 . Results indicated remarkable faradaic efficiency for 1-butanol formation of 3.868%. This study provides a perspective on the C−C coupling reaction on Cu-based electrocatalysts for the electroreduction of CO 2 into high-value multicarbon products.

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