The direct acetalization of ethanol is a significant challenge for upgrading bioethanol to value-added chemicals. In this study, 1,1-diethoxyethane (DEE) is selectively synthesized by the electrolysis of ethanol using a proton-exchange membrane (PEM) reactor. In the PEM reactor, a Pt/C catalyst promoted the electro-oxidation of ethanol to acetaldehyde. The Nafion membrane used as the PEM served as a solid acid catalyst for the acetalization of ethanol and electrochemically formed acetaldehyde. DEE was obtained at high faradaic efficiency (78 %) through sequential electrochemical and nonelectrochemical reactions. The DEE formation rate through PEM electrolysis was higher than that of reported systems. At the cathode, protons extracted from ethanol were reduced to H . The electrochemical approach can be utilized as a sustainable process for upgrading bioethanol to chemicals because it can use renewable electricity and does not require chemical reagents (e. g., oxidants and electrolytes).
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