Electronic and geometric interactions between active and support phases are critical in determining the activity of heterogeneous catalysts, but metal-support interactions are challenging to study. Here, it is demonstrated how the combination of the monolayer-controlled formation using atomic layer deposition (ALD) and colloidal nanocrystal synthesis methods leads to catalysts with sub-nanometer precision of active and support phases, thus allowing for the study of the metal-support interactions in detail. The use of this approach in developing a fundamental understanding of support effects in Pd-catalyzed methane combustion is demonstrated. Uniform Pd nanocrystals are deposited onto Al₂ O₃ /SiO₂ spherical supports prepared with control over morphology and Al₂ O₃ layer thicknesses ranging from sub-monolayer to a ≈4 nm thick uniform coating. Dramatic changes in catalytic activity depending on the coverage and structure of Al₂ O₃ situated at the Pd/Al₂ O₃ interface are observed, with even a single monolayer of alumina contributing an order of magnitude increase in reaction rate. By building the Pd/Al₂ O₃ interface up layer-by-layer and using uniform Pd nanocrystals, this work demonstrates the importance of controlled and tunable materials in determining metal-support interactions and catalyst activity.

Stable catalysts are essential to address energy and environmental challenges, especially for applications in harsh environments (for example, high temperature, oxidizing atmosphere and steam). In such conditions, supported metal catalysts deactivate due to sintering-a process where initially small nanoparticles grow into larger ones with reduced active surface area-but strategies to stabilize them can lead to decreased performance. Here we report stable catalysts prepared through the encapsulation of platinum nanoparticles inside an alumina framework, which was formed by depositing an alumina precursor within a separately prepared porous organic framework impregnated with platinum nanoparticles. These catalysts do not sinter at 800 °C in the presence of oxygen and steam, conditions in which conventional catalysts sinter to a large extent, while showing similar reaction rates. Extending this approach to Pd-Pt bimetallic catalysts led to the small particle size being maintained at temperatures as high as 1,100 °C in air and 10% steam. This strategy can be broadly applied to other metal and metal oxides for applications where sintering is a major cause of material deactivation.