Guiding CO2RR Selectivity by Compositional Tuning in the Electrochemical Double Layer

The electrochemical conversion of carbon dioxide to value-added chemicals provides an environmentally benign alternative to current industrial practices. However, current electrocatalytic systems for the CO₂ reduction reaction (CO₂RR) are not practical for industrialization, owing to poor specific product selectivity and/or limited activity. Interfacial engineering presents a versatile and effective method to direct CO₂RR selectivity by fine-tuning the local chemical dynamics. This Account describes interfacial design strategies developed in our laboratory that use electrolyte engineering and porous carbon materials to modify the local composition at the electrode-electrolyte interface.Our first strategy for influencing surface reactivity is to perturb the electrochemical double layer by tuning the electrolyte composition. We approached this investigation by considering how charged molecular additives can organize at the electrode surface and impact CO₂ activation. Using a combination of advanced electrochemical techniques and in situ vibrational spectroscopy, we show that the surfactant properties (the identity of the headgroup, alkyl chain length, and concentration) as well as the electrolyte cation identity can affect how surfactant molecules assemble at a biased electrode. The interplay between the electrolyte cations and the surfactant additives can be regulated to favor specific carbon products, such as HCOO^-, and suppress the parasitic hydrogen evolution reaction (HER). Together, our findings highlight how molecular assemblies can be used to design selective electrocatalytic systems.In addition to the electrolyte design, the local spatial confinement of reaction intermediates presents another strategy to direct CO₂RR selectivity. We were interested in uncovering the role of porous carbon-supported catalysts toward selective carbon product formation. In our initial study, we show that carbon porosity can be optimized to enhance C₂H₄ and CO selectivity in a series of Cu catalysts embedded in a tunable carbon aerogel matrix. These results suggested that local confinement of the active surface plays a role in CO₂ activation and motivated an investigation into probing how this phenomenon can be translated to a planar Cu electrode. Our findings show that carbon modifiers facilitated surface reconstruction and regulated CO₂ diffusion to suppress HER and improve the C_2-3 product selectivity. Given the ubiquity of carbon materials in catalysis, this work demonstrates that carbon plays an active role in regulating selectivity by restricting the diffusion of substrate and reaction intermediates. Our work in tuning the composition of the electrochemical double layer for increased CO₂RR selectivity demonstrates the potential versatility in boosting catalytic performance across an array of catalytic systems.