High‐Entropy Alloy Aerogels: A New Platform for Carbon Dioxide Reduction

High-entropy alloy aerogels (HEAAs) combined with the advantages of high-entropy alloys and aerogels are prospective new platforms in catalytic reactions. However, due to the differences in reduction potentials and miscibility behavior of different metals, the realization of HEAAs with a single phase is still a great challenge. Herein, a series of HEAAs is fabricated via the freeze-thaw method as highly active and durable electrocatalysts for the carbon dioxide reduction reaction (CO₂ RR). Especially, the PdCuAuAgBiIn HEAAs can achieve Faradaic efficiency (FE) of C1 products almost 100% from -0.7 to -1.1 V versus reversible hydrogen electrode (V_RHE ), and a maximum FE for formic acid (FE_HCOOH ) of 98.1% at -1.1 V_RHE , outperforming PdCuAuAgBiIn high-entropy alloy particles (HEAPs) and Pd metallic aerogels (MAs). Specifically, the current density and FE_HCOOH are almost 200 mA cm^-2 and 87% in a flow cell. The impressive CO₂ RR performance of the PdCuAuAgBiIn HEAAs is attributed to the strong interactions between the different metals and the surface unsaturated sites, which can regulate the electronic structures of different metals and allow the optimal HCOO* intermediate adsorption and desorption onto the catalysts surface to enhance HCOOH production. The work not only provides a facile synthetic strategy to fabricate HEAAs, but also opens the avenue for development of efficient catalysts and beyond.