Designing Supported Nanoparticles via Synergistic Ex‐Solution and Phosphorization for Tailored Active Site Generation

Supported nanoparticles incorporating catalytically attractive nonmetal elements have gained significant attention as a promising strategy for enhancing catalytic activity in various industrial applications. This study presents an innovative one-pot synthesis method for fabricating hybrid catalysts, which simultaneously modifies surface properties through the precipitation of nanoparticles with the concurrent incorporation of nonmetal elements. The underlying concept is to synchronize the temperature required for particle formation with that of nonmetal incorporation by adjusting the oxygen chemical potential of the host oxide. As a case study, Ir- and Ru-doped WO₃ are selected as the starting material, with phosphorus (P) as the representative nonmetal for surface functionalization. Notably, the hybrid catalyst, composed of amorphous (Ir,Ru)P_x particles dispersed on P-rich WO_2.9 sheets, is synthesized through a single heat treatment at 500 °C, avoiding undesirable sintering of the host material. When used as a hydrogen evolution catalyst, this material exhibits outstanding mass activity, durability, compared to state-of-the-art Pt/C catalysts. Density functional theory calculations further reveal that the superior performance of the hybrid catalysts attributes to improved water dissociation and favorable adsorption and desorption of key reaction intermediates. This novel synthesis strategy offers considerable potential for advancing diverse areas of heterogeneous catalysis.