Fluorine-mediated regulation: empowering high-performance electrocatalysts for CO₂ electroreduction

The electrocatalytic reduction of carbon dioxide (CO₂RR) is a promising technology for sustainable fuel and chemical production, offering a dual solution for climate change mitigation and carbon resource recycling. Nevertheless, the practical deployment of CO₂RR is limited by some inherent bottlenecks, including low product selectivity, high overpotentials, and inadequate long-term stability. Recent investigations have demonstrated that fluorine-related modification possesses distinctive merits to boost CO₂RR performance, such as tuning the electronic structure and interfacial microenvironment of catalysts. Most notably, it enables effective stabilization of high-valence active centers and regulation of catalyst dynamic reconstruction under cathodic conditions, offering advantages that can complement or, in some cases, outperform conventional modification strategies. However, fluorine modification also faces challenges, including potential trade-offs between hydrophobicity and mass transport, and limited scalability of current fluorination methods. A specialized review summarizing recent advances remains lacking. To fill this gap and provide a roadmap for rational catalyst design, this review summarizes the state-of-the-art progress of fluorine-modified CO₂RR catalysts, including carbon materials, fluorine-doped metal catalysts, and organic substrate-modulated composite catalysts, aiming to clarify the structure-activity relationships. It also outlines the challenges and prospects associated with fluorine modification for CO₂RR.