Lawrence Berkeley National Laboratory

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.