Templating Bicarbonate in the Second Coordination Sphere Enhances Electrochemical CO ₂ Reduction Catalyzed by Iron Porphyrins

Bicarbonate-based electrolytes are ubiquitous in aqueous electrochemical CO₂ reduction, particularly in heterogenous catalysis, where they demonstrate improved catalytic performance relative to other buffers. In contrast, the presence of bicarbonate in organic electrolytes and its roles in homogeneous electrocatalysis remain underexplored. Here, we investigate the influence of bicarbonate on iron porphyrin-catalyzed electrochemical CO₂ reduction. We show that bicarbonate is a viable proton donor in organic electrolyte (p<i>K</i>_a = 20.8 in dimethyl sulfoxide) and that urea pendants in the second coordination sphere can be used to template bicarbonate in the vicinity of a molecular iron porphyrin catalyst. The templated binding of bicarbonate increases its acidity, resulting in a 1500-fold enhancement in catalytic rates relative to unmodified parent iron porphyrin. This work emphasizes the importance of bicarbonate speciation in wet organic electrolytes and establishes second-sphere bicarbonate templating as a design strategy to harness this adventitious acid and enhance CO₂ reduction catalysis.