Using Light and Electrons to Bend Carbon Dioxide: Developing and Understanding Catalysts for CO2 Conversion to Fuels and Feedstocks (2022)

Our global society generates an unwieldy amount of CO<sub>2</sub> 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 CO<sub>2</sub> 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 CO<sub>2</sub> 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 CO<sub>2</sub> to formate at electrocatalytic indium and tin electrodes. These studies demonstrated the key role of surface oxides in catalyzing the reduction of CO<sub>2</sub>. 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 Cr<sub>3</sub>Ga 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 CO<sub>2</sub> in aqueous electrolyte. These studies demonstrated that electrodes that normally yield a low hydrogen overpotential (Pd and Pt) show suppressed H<sub>2</sub> evolution and strongly enhanced activity for CO<sub>2</sub> 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 CO<sub>2</sub> 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 CO<sub>2</sub>, stimulating our interest in the chemistry of MnBr(bpy)(CO)<sub>3</sub> and related compounds. This complex was reported to electrochemically reduce CO<sub>2</sub> to CO. We saw these reports as an opportunity to study the detailed nature of the proton-coupled electron transfer (PCET) mechanism associated with CO<sub>2</sub> reduction. Our investigation of this system revealed the role of hydrogen-bonding in CO<sub>2</sub> reduction and pointed the way for the construction of a photochemical process for CO generation using a [(bpy)(CO)<sub>3</sub>Mn(CN)Mn(bpy)(CO)<sub>3</sub>]<sup>+</sup> photocatalyst.Based on our studies to date, it appears likely that heterogeneous systems can be assembled to convert CO<sub>2</sub> 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 CO<sub>2</sub>.