Our global society generates an unwieldy amount of CO₂ per unit time. Therefore, the capture of this greenhouse gas must involve a diverse set of strategies. One solution to this problem is the conversion of CO₂ into a more useful chemical species. Again, a multiplicity of syntheses and products will be necessary. No matter how elegant the chemistry is, commercial markets often have little use for a small set of compounds made in tremendous yield. Following this reasoning, the Bocarsly Research Group seeks to develop new electrochemical and photochemical processes that may be of utility in the conversion of CO₂ to organic compounds. We focus on investigating proton-coupled charge transfer mechanisms that produce both C1 and carbon-carbon bonded products (C2+).In early work, we considered the reduction of CO₂ to formate at electrocatalytic indium and tin electrodes. These studies demonstrated the key role of surface oxides in catalyzing the reduction of CO₂. This work generated efficient systems for the formation of formate and paved the way to studies using non-copper, intermetallic electrocatalysts for the generation of C2+ species. Most notable is the efficient formation of oxalate at an oxidized Cr₃Ga electrode. Oxalate has recently been suggested as a potential nonfossil, alternate organic feedstock.Separately, we have focused on the electrocatalytic effects of pyridine on the reduction of CO₂ in aqueous electrolyte. These studies demonstrated that electrodes that normally yield a low hydrogen overpotential (Pd and Pt) show suppressed H₂ evolution and strongly enhanced activity for CO₂ reduction in the presence of pyridinium. Methanol was observed to form in high Faradaic yield at low overpotential using this system. The 6-electron, 6-proton reduction of CO₂ in the presence of pyridinium was intriguing, and significant effort was placed on understanding the mechanism of this reaction both on metal electrodes and on semiconducting photocathodes. P-GaP electrodes were found to provide exceptional behavior for the formation of methanol using only light as the energy source.The pyridinium studies highlighted the role of protons in the overall reduction of CO₂, stimulating our interest in the chemistry of MnBr(bpy)(CO)₃ and related compounds. This complex was reported to electrochemically reduce CO₂ to CO. We saw these reports as an opportunity to study the detailed nature of the proton-coupled electron transfer (PCET) mechanism associated with CO₂ reduction. Our investigation of this system revealed the role of hydrogen-bonding in CO₂ reduction and pointed the way for the construction of a photochemical process for CO generation using a [(bpy)(CO)₃Mn(CN)Mn(bpy)(CO)₃]⁺ photocatalyst.Based on our studies to date, it appears likely that heterogeneous systems can be assembled to convert CO₂ into products that are "beyond C2 products." This may open up new practical chemistry in the area of fossil-based replacements for both synthesis and fuels. Systems with pragmatic efficiencies are close to reality. Electrochemical reactors using heterogeneous electrocatalysts show the stability and product selectivity needed to generate industrial opportunities. Continued growth of mechanistic understanding is expected to facilitate the chemical design of cogent systems for the taming of CO₂.

Kailyn Y. Cohen

Publications