Sulfur-Rich Benzothiadiazole-Based Conjugated Polymers for Efficient CO ₂ Electroreduction

The development of metal-free organic electrocatalysts for CO2 reduction remains a significant challenge, requiring materials with well-defined structures and superior electrochemical properties. In this study, we present the rational design and synthesis of a benzothiadiazole-based conjugated polymer (OAP), demonstrating its potential as a highly efficient and solution-processable metal-free electrocatalyst for CO2 reduction. Computational and experimental studies confirm strong CO2 interactions, while electrochemical measurements reveal that OAP1 achieves a Faradaic efficiency (C1+C2) of 15.41%, which increases to 45%, with the addition of a cocatalyst, outperforming nitrogen-containing polymer electrocatalysts. The superior performance of OAP1 is attributed to its enhanced charge transfer capability and increased density of exposed active sites, as evidenced by density functional theory studies. These findings highlight the potential of OAP as a promising candidate for sustainable CO2 electroreduction, facilitating the design of next-generation sulfur-containing catalysts.