CO2 Electroreduction on Unsupported PdPt Aerogels: Effects of Alloying and Surface Composition on Product Selectivity

Due to its unique ability to reduce carbon dioxide (CO2) into CO or formate at high vs. low overpotentials, respectively, palladium is a promising catalyst for the electrochemical CO2-reduction reaction (CO2RR).Further improvements aim at increasing its activity and selectivity toward either of these value-added species while reducing the amount of hydrogen produced as a side-product.With this motivation, in this work, we synthesized a range of unsupported, bimetallic PdPt-as well as pure Pt-or Pd-aerogels and extensively characterized them using various microscopic and spectroscopic techniques.These revealed that the aerogels' porous web consists of homogenous alloys of Pt and Pd, with palladium and platinum being present on their surface for all compositions.The subsequent determination of these aeorgels' CO2RR-performance unveiled that the high activity of these Pt surface atoms toward hydrogen evolution causes all PdPt alloys to favor this reaction over CO2-reduction.In the case of the pure Pd aerogel, though, its unsupported nature leads to a suppression of H2-evolution and a concomitant increase in the selectivity toward CO when compared to a commercial, carbon-supported Pd-nanoparticle catalyst.