Autocatalytic Formation of High‐Entropy Alloy Nanoparticles

High‐entropy alloy (HEA) nanoparticles hold great promise as tunable catalysts. Despite the fact that alloy formation is typically difficult in oxygen‐rich environments, we found that Pt‐Ir‐Pd‐Rh‐Ru nanoparticles can be synthesized under benign low‐temperature solvothermal conditions. In situ X‐ray scattering and transmission electron microscopy reveal the solvothermal formation mechanism of Pt‐Ir‐Pd‐Rh‐Ru nanoparticles. For the individual metal acetylacetonate precursors, formation of single metal nanoparticles takes place at temperatures spanning from ca. 150 °C for Pd to ca. 350 °C for Ir. However, for the mixture, homogenous Pt‐Ir‐Pd‐Rh‐Ru HEA nanoparticles can be obtained around 200 °C due to autocatalyzed metal reduction at the (111) facets of the forming crystallites. The autocatalytic formation mechanism suggests that many types of HEA nanocatalysts should accessible with scalable solvothermal reactions, thereby providing broad availability and tunability. High‐entropy alloy (HEA) nanoparticles hold great promise as tunable catalysts, and surprisingly, Pt‐Ir‐Pd‐Rh‐Ru nanoparticles can be synthesized under benign low‐temperature solvothermal conditions. In situ X‐ray scattering and TEM reveal the solvothermal formation mechanism of Pt‐Ir‐Pd‐Rh‐Ru nanoparticles. The autocatalytic formation mechanism suggests that many types of HEA nanocatalysts should be accessible with scalable solvothermal reactions.