Triad of electrocatalytic strategies for polymer monomer synthesis

Abstract

Electrocatalysis provides a green and scalable route for synthesizing polymer monomers directly from renewable feedstocks such as water, CO₂, and biomass derivatives. This review delineates the evolution of electrocatalytic strategies, presenting a progressively advancing framework, from elementary transformations to integrated catalytic systems. The strategies discussed represent different stages of this evolution: (i) primary aqueous electrochemical transformations driven by in situ generated *H or ⁻OH species for producing monomers such as adipic acid, lactic acid, and ethylene; (ii) coupling electrocatalytic transformations, in which electrochemically generated electrophilic or nucleophilic intermediates undergo C–N or C–C coupling to yield complex monomers like cyclohexanone oxime; and (iii) cascade electrocatalytic systems integrating biocatalysis, thermocatalysis, or photocatalysis to enable the synthesis of longer-chain polymer monomers. Emphasis is placed on universal catalyst design principles – including coordination environment regulation, electronic structure modulation, and interfacial microenvironment engineering – as well as mechanistic insights from in situ characterization and theoretical modeling. In addition, this review introduces techno-economic analysis (TEA) and life-cycle assessment (LCA) to evaluate the energy consumption and economic viability of electrocatalytic systems, and further discusses the critical impact of product separation and purification on overall energy efficiency and process feasibility. Finally, perspectives are provided on the future development of renewable monomer electrosynthesis for sustainable polymer production.