Scalable two-step annealing method for preparing ultra-high-density single-atom catalyst libraries (vol 17, pg 174, 2022)

A general versatile approach combining wet-chemistry impregnation and two-step annealing is devised for the scalable synthesis of a library of ultra-high-density single-atom catalysts with drastically enhanced reactivity. The stabilization of transition metals as isolated centres with high areal density on suitably tailored carriers is crucial for maximizing the industrial potential of single-atom heterogeneous catalysts. However, achieving single-atom dispersions at metal contents above 2 wt% remains challenging. Here we introduce a versatile approach combining impregnation and two-step annealing to synthesize ultra-high-density single-atom catalysts with metal contents up to 23 wt% for 15 metals on chemically distinct carriers. Translation to a standardized, automated protocol demonstrates the robustness of our method and provides a path to explore virtually unlimited libraries of mono- or multimetallic catalysts. At the molecular level, characterization of the synthesis mechanism through experiments and simulations shows that controlling the bonding of metal precursors with the carrier via stepwise ligand removal prevents their thermally induced aggregation into nanoparticles. The drastically enhanced reactivity with increasing metal content exemplifies the need to optimize the surface metal density for a given application. Moreover, the loading-dependent site-specific activity observed in three distinct catalytic systems reflects the well-known complexity in heterogeneous catalyst design, which now can be tackled with a library of single-atom catalysts with widely tunable metal loadings.