Atom-by-Atom Synthesis of Multiatom-Supported Catalytic Clusters by Liquid-Phase Atomic Layer Deposition

Here, we introduce a method for the synthesis of atomically precise, supported, multiatom catalysts by liquid-phase atomic layer deposition. This technique is based on consecutive grafting reactions in mild conditions that build supported active sites atom by atom. The atomically controlled synthesis procedure led to the growth of well-defined multinuclear (Al, Mg, Si, Zn, and O) clusters. The composition of the clusters was verified by titrations ICP-OES, STEM-EDX, and XPS, while their structure was resolved from the synthesis sequence, elemental composition, and extensive characterization (X-ray absorption, solid-state NMR, STEM, XPS, and DFT calculations). Propane dehydrogenation was used as a probe reaction to demonstrate the potential to control and tailor the activity and stability of these catalytic clusters. Notably, we were able to alternatively multiply the initial activity of a known single-atom catalyst by 6 fold or improve its stability against thermal deactivation by simply using different elements and modifying the deposition sequence.