Bottom-up assembly of bimetallic nanocluster catalysts from oxide-supported single-atom precursors

The precise synthesis and stabilization of oxide-supported bimetallic clusters in the low-to-sub nanometer size regime is highly relevant in various fields, from optics and sensing to electrochemistry and catalysis. In surface-driven phenomena such as catalysis, avoiding metal segregation and agglomeration is essential for performance and stability under relevant operation conditions. Here we show how high-temperature oxidative crystal redispersion and oxide atom-trapping phenomena provide a widely valid route towards atomically dispersed bimetallic precursors which, upon reductive metal agglomeration, result in very small, uniformly sized and remarkably stable bimetallic clusters. For a PdPt/MgO system, oxidative redispersion leads to isolated Pd and Pt atoms stabilized by the MgO support up to overall surface metal contents of ca. 1.0 M-at nm(-2), beyond which loading, atom-trapping oxide sites become exhausted and metal aggregation sets in. On the contrary, more conventional, milder-temperature activation protocols lead to significant metal segregation and markedly bimodal particle size populations already from comparatively lower metal contents. As proven by in situ X-ray absorption spectroscopy and atomic-resolution STEM microscopy, the stabilization of isolated Pd and Pt cations within nanometer distances on the common MgO support is essential for the synthesis of ca. 1 nm bimetallic PdPt clusters by reductive agglomeration. The uniformly sized PdPt aggregates developed on MgO from single-atom precursors display a notably higher activity for the oxidative activation of methane with carbon dioxide (dry reforming) at 923 K compared to analogue materials synthesized via milder calcination/reduction protocols. Moreover, despite their high surface-to-volume ratio, the small bimetallic clusters in the former display an outstanding stability against metal agglomeration under the demanding reaction conditions, likely as a result of a lower driving force for Ostwald ripening growth processes. The synthesis concept, which is amenable to other combinations of 4d and 5d transition metals, contributes to the rationalization of the possibilities and bounds of oxidative metal redispersion phenomena and provides a technically simple and potentially general route to high-temperature stable, (sub)nanometer bimetallic clusters for catalysis and other applications where bimetallic effects and thermal stability are of importance.