Single-Atom Catalysts through Pressure-Controlled Metal Diffusion.

ABSTRACT

Single-atom catalysts (SACs) open up new possibilities for advanced technologies. However, a major complication in preparing high-density single-atom sites is the aggregation of single atoms into clusters. This complication stems from the delicate balance between the diffusion and stabilization of metal atoms during pyrolysis. Here, we present pressure-controlled metal diffusion as a new concept for fabricating ultra-high-density SACs. Reducing the pressure inhibits aggregation substantially, resulting in almost three times higher single-atom loadings than those obtained at ambient pressure. Molecular dynamics and computational fluid dynamics simulations reveal the role of a metal hopping mechanism, maximizing the metal atom distribution through an increased probability of metal-ligand binding. The investigation of the active site density by electrocatalytic oxygen reduction validates the robustness of our approach. The first realization of Ullmann-type carbon-oxygen couplings catalyzed on single Cu sites demonstrates further options for efficient heterogeneous catalysis.