Coupling Alternative Anodic Reactions in Electrochemical Valorization

Electrochemical valorization of small molecules such as H 2 O, CO 2, and N 2 into value-added products represents a sustainable strategy to mitigate greenhouse gas emissions and store intermittent renewable energy in high-energy-density chemicals. Traditionally, these processes couple with the water oxidation reaction at the anode, which unfortunately suffers from high overpotentials and thus limits the overall energy efficiency. Over the past decade, alternative anodic reactions have been explored to improve energy efficiency and enhance the product value. Despite their potential, significant technical challenges remain before practical implementation can be realized. In this Perspective, we briefly overview the current status of coupling alternative anodic reactions for the electrochemical valorization of small molecules and discuss the key challenges and potential solutions from the viewpoints of catalyst design, electrolyzer engineering, and product separation. We aim to highlight how these advances collectively pave the way toward more energy-efficient, economically viable, and sustainable electrochemical manufacturing.