Porous alumina protective coatings on palladium nanoparticles by self-poisoned atomic layer deposition

Atomic layer deposition (ALD) of Al ₂O ₃ using trimethylaluminum (TMA) and water on Pd nanoparticles (NPs) was studied by combining in situ quartz crystal microbalance (QCM) measurements, in situ quadrupole mass spectrometry (QMS), and transmission electron microscopy (TEM) with density functional theory (DFT) calculations. TEM images of the ALD Al ₂O ₃ overcoated Pd showed conformal Al ₂O ₃ films on the Pd NPs as expected for ALD. However, hydrogen detected by in situ QMS during the water pulses suggested that the ALD Al ₂O ₃ films on the Pd NPs were porous rather than being continuous coatings. Additional in situ QCM and QMS measurements indicated that Al ₂O ₃ ALD on Pd NPs proceeds by a self-poisoning, self-cleaning process. To evaluate this possibility, DFT calculations were performed on Pd(111) and Pd(211) as idealized Pd NP surfaces. These calculations determined that the TMA and water reactions are thermodynamically favored on the stepped Pd(211) surface, consistent with previous observations. Furthermore, the DFT studies identified methylaluminum (AlCH ₃*, where the asterisk designates a surface species) as the most stable intermediate on Pd surfaces following the TMA exposures, and that AlCH ₃* transforms into Al(OH) ₃* species during the subsequent water pulse. The gas phase products observed using in situ QMS support this TMA dissociation/hydration mechanism. Taken together, the DFT and experimental results suggest a process in which the Pd surface becomes poisoned by adsorbed CH ₃* species during the TMA exposures that prevent the formation of a complete monolayer of adsorbed Al species. During the subsequent H ₂O exposures, the Pd surface is cleaned of CH ₃* species, and the net result is a porous Al ₂O ₃ film. This porous structure can retain the catalytic activity of the Pd NPs by providing reagent gases with access to the Pd surface sites, suggesting a promising route to stabilize active Pd catalysts.