Electrocarboxylation of CO₂ with Organic Substrates: Toward Cathodic Reaction

Abstract

Electrocarboxylation of carbon dioxide (CO₂) using organic substrates has emerged as a promising method for the sustainable synthesis of value-added carboxylic acids due to its renewable energy source and mild reaction conditions. The reactivity and product selectivity of electrocarboxylation are highly dependent on the cathodic behavior, involving a sequence of electron transfers and chemical reactions. Hence, it is necessary to understand the cathodic reaction mechanisms for optimizing reaction performance and product distribution. In this work, a review of recent advancements in the electrocarboxylation of CO₂ with organic substrates based on different cathodic reaction pathways is presented to provide a reference for the development of novel methodologies of CO₂ electrocarboxylation. Herein, cathodic reactions are particularly classified into two categories based on the initial electron carriers (i.e., CO₂ radical anion and substrate radical anion). Furthermore, three cathodic pathways (ENE(N), ENED, and EDEN) of substrate radical anion-induced electrocarboxylation are discussed, which differ in their electron transfer sequence, substrate dissociation, and nucleophilic reaction, to highlight their implications on reactivity and product selectivity.

Keywords

Carbon dioxide / Electrocatalysis / Carboxylation / Cathodic reaction / Carboxylic acids

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