Design and Properties of Confined Nanocatalysts by Atomic Layer Deposition

Governing the process and outcome of chemical reactions is the most important aim of catalytic chemistry. The confinement of active sites inside nanosized spaces provides a powerful strategy to achieve this goal. Reacting molecules (reactants, intermediates, and products of a reaction) and nanomaterials (metal/metal-oxide nanoparticles) confined inside nanoreactors have been observed to exhibit modified behaviors and properties with respect to their unconfined counterparts. Typically, catalysts confined in zeolites, mesoporous materials, metal-organic frameworks, and nanotubes are obtained by traditional liquid-phase methods. However, excess metals or undesired solvents and other reagents must be removed. It is also difficult to precisely regulate the confined nanostructures and assemble multifunctional sites in the confined nanospaces. Atomic layer deposition (ALD) provides a controllable method to fabricate confined catalysts due to its outstanding advantages. In this Account, we describe our progress in the design and properties of confined nanocatalysts by ALD. ALD is an elegant method to directly deposit highly dispersed metal or oxide species into porous materials, including zeolites and mesoporous materials. We deposited Pt nanoclusters in the micropores of a KL zeolite with precisely controlled size by ALD. We also introduced CoO_x nanoclusters into mesoporous SBA-15. We have reported pioneering works on the synthesis of confined nanoparticles with metal-in-nanotube structures by a template-assisted ALD method. Confined Cu nanoparticles were prepared by reducing CuO nanowires coated with Al₂O₃, TiO₂, or alucone layers by ALD. Confined Cu and Au nanoparticles were also prepared starting from the corresponding metal nanowires with the assistance of sacrificial layers produced by ALD. In a more facile strategy, Au nanoparticles confined in Al₂O₃ nanotubes were produced using a sacrificial template by ALD. Furthermore, we synthesized a multiply confined Ni-based nanocatalyst through a template-assisted ALD method. We assembled multiple interfaces (Ni/Al₂O₃ and Pt/TiO₂) in a confined nanospace for tandem reactions by template-assisted ALD. The synergistic effect of two interfaces enhanced the tandem reaction, and the confined nanospace favored the instant transfer of intermediates between the two interfaces. In addition, porous TiO₂ nanotubes with spatially separated Pt and CoO_x cocatalysts were also produced by ALD. The confined catalysts can be further treated by ALD. We used ALD to modify the mesoporous SBA-15 support to precisely tune the active species-support interaction. In addition to the support, the confined metal nanoparticles can also be coated with an ultrathin oxide layer by ALD to further improve their catalytic activities. Moreover, the structure and size of the confined nanospace can be tuned precisely by ALD. Overall, ALD has exhibited noteworthy applications in and will provide new opportunities for the design and synthesis of highly effective confined catalysts.