Hydrogen spillover-driven synthesis of high-entropy alloy nanoparticles as a robust catalyst for CO2 hydrogenation.

High-entropy alloys (HEAs) have been intensively pursued as potentially advanced materials because of their exceptional properties. However, the facile fabrication of nanometer-sized HEAs over conventional catalyst supports remains challenging, and the design of rational synthetic protocols would permit the development of innovative catalysts with a wide range of potential compositions. Herein, we demonstrate that titanium dioxide (TiO2) is a promising platform for the low-temperature synthesis of supported CoNiCuRuPd HEA nanoparticles (NPs) at 400 °C. This process is driven by the pronounced hydrogen spillover effect on TiO2 in conjunction with coupled proton/electron transfer. The CoNiCuRuPd HEA NPs on TiO2 produced in this work were found to be both active and extremely durable during the CO2 hydrogenation reaction. Characterization by means of various in situ techniques and theoretical calculations elucidated that cocktail effect and sluggish diffusion originating from the synergistic effect obtained by this combination of elements. Facile fabrication of high-entropy alloys (HEAs) nanoparticles (NPs) on conventional catalyst supports remains challenging. Here the authors show TiO2 is a promising platform for the low-temperature synthesis of supported CoNiCuRuPd HEA NPs with excellent activity and durability in CO2 hydrogenation.