Review on Electrocatalytic Carbon Dioxide Reduction to Hydrocarbons and Fuels

Abstract The electrocatalytic reduction of carbon dioxide (CO2RR) has emerged as a promising strategy to mitigate rising atmospheric CO2 levels while simultaneously producing value-added fuels and chemical building blocks for plastics and pharmaceuticals. This review provides a comprehensive roadmap integrating fundamental reaction principles, catalyst architectures, and techno-economic perspectives to guide CO2RR from laboratory demonstrations to scalable technologies. We highlight the fundamental thermodynamic and kinetic barriers of CO2 activation, the influence of the electrical double layer, and the persistent challenge of the competing hydrogen evolution reaction. The review systematically classifies electrocatalysts by product selectivity, emphasizing the unique role of copper in enabling C–C coupling for C2+ hydrocarbons, alongside the synergistic effects of bimetallic and tandem systems. Advanced architectures, including single-atom catalysts, defect engineering, and hetero-structured materials, are discussed for their ability to enhance selectivity, activity, and stability. Reaction pathways are analyzed to elucidate mechanisms for C1 and C2+ products. Finally, the transition from H-cell configurations to gas diffusion electrodes is reviewed as a critical step toward industrial current densities, positioning CO2RR as a cornerstone of a sustainable carbon economy.