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The electroreduction of crotonaldehyde, which can be derived from the aldol condensation of acetaldehyde (sustainably produced from CO2 reduction or from biomass ethanol), is potentially a carbon‐neutral route for generating high‐value C4 chemicals such as crotyl alcohol and 1‐butanol. Developing functional catalysts is necessary toward this end. Herein, the electrocatalytic conversion of crotonaldehyde to crotyl alcohol and 1‐butanol was achieved in 0.1 m potassium phosphate buffer electrolyte (pH=7). More importantly, the mechanisms and structure‐activity relationships of these transformations were elucidated. Crotyl alcohol was formed on oxide‐derived Ag at −0.75 V versus the reversible hydrogen electrode (RHE) with a faradaic efficiency (FE) of 84.3 % (reactant conversion after 75 min electrolysis=9.8 %), which is 1.6 times higher than that on polished Ag foils. The coordinatively‐unsaturated sites on oxide‐derived Ag surfaces were proposed to facilitate crotonaldehyde adsorption via its oxygen atom in order to promote crotyl alcohol formation. On electrodeposited Fe nanoflakes, crotonaldehyde could be reduced to 1‐butanol with an outstanding FE of 60.6 % (reactant conversion after 75 min electrolysis=9.4 %) at −0.70 V vs. RHE. This is nearly 3 times higher than the FE of 1‐butanol observed on polished Fe foils at the same potential. More strikingly, the corresponding partial current density of 1‐butanol was −9.19 mA cm−2, which is 43 times higher than that on Fe foils. The presence of tensile strains and grain boundaries on the Fe nanoflakes were elucidated and suggested to activate a concerted reduction of the C=O and C=C bonds in crotonaldehyde to produce 1‐butanol selectively. [ABSTRACT FROM AUTHOR]

The electroreduction of carbon dioxide using renewable electricity is an appealing strategy for the sustainable synthesis of chemicals and fuels. Extensive research has focused on the production of ethylene, ethanol and n‐propanol, but more complex C4 molecules have been scarcely reported. Herein, we report the first direct electroreduction of CO2 to 1‐butanol in alkaline electrolyte on Cu gas diffusion electrodes (Faradaic efficiency=0.056 %, j1‐Butanol=−0.080 mA cm−2 at −0.48 V vs. RHE) and elucidate its formation mechanism. Electrolysis of possible molecular intermediates, coupled with density functional theory, led us to propose that CO2 first electroreduces to acetaldehyde‐a key C2 intermediate to 1‐butanol. Acetaldehyde then undergoes a base‐catalyzed aldol condensation to give crotonaldehyde via electrochemical promotion by the catalyst surface. Crotonaldehyde is subsequently electroreduced to butanal, and then to 1‐butanol. In a broad context, our results point to the relevance of coupling chemical and electrochemical processes for the synthesis of higher molecular weight products from CO2. [ABSTRACT FROM AUTHOR]