ABSTRACT Electrochemical conversion of biomass and carbon dioxide (CO 2 ) to sustainable chemicals offers advantages over thermochemical methods through lower reaction temperatures, higher selectivity, and compatibility with renewable energy. Thermodynamics also offers a domain‐specific framework for assessing the viability and efficiency of these steps by evaluating the energy requirements, pathways, and restrictions imposed by catalysis. Therefore, this review aims to provide a comprehensive thermodynamic perspective on electrochemical biomass oxidation and CO 2 reduction, addressing Gibbs free energy, redox potentials, pH‐dependent Nernst relations, and free‐energy landscapes. Moreover, the relevance of multielectron and proton‐coupled reactions, overpotential demands, the stability of intermediates, and alternative pathways were discussed. Additionally, progress in electrocatalyst design, paired electrolysis configurations, and electrolyte engineering, which conceptually respond to thermodynamic limits, was highlighted. Finally, the review explores various strategies for co‐electrolyzing biomass and CO 2 , which can improve atom economy and overall process efficiency. The insights provided are intended to support further advancements toward energy‐efficient, highly selective, and sustainable chemical synthesis pathways aligned with carbon‐neutral goals.
Ourimi et al. (Wed,) studied this question.
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