Importance of Size and Contact Structure of Gold Nanoparticles for the Genesis of Unique Catalytic Processes

Since the discovery of catalysis by Au nanoparticles (NPs), unique catalytic features of Au have appeared that are greatly different from those of Pd and Pt. In this Review, we aimed to disclose how the unique catalytic abilities of Au are generated with respect to (a) the contact structures between Au and its supports and (b) the size of the Au particles. For CO oxidation, the catalytic activity of Au on reducible metal oxides (MO) is strongly correlated with the amount of oxygen vacancies of the MO surface, which play a key role in O₂ activation. Single atoms, bilayers of Au, sub-nm clusters, clusters (1-2 nm), and NPs (2-5 nm) have been proposed as the active sizes of the Au species, which may depend on the type of support. For propylene epoxidation, the presence of isolated TiO₄ units in SiO₂ supports is important for the production of propylene oxide (PO). Au NPs facilitate the formation of Ti-OOH species, which leads to PO in the presence of H₂ and O₂, whereas Au clusters facilitate propylene hydrogenation. However, Au clusters can produce PO by using only O₂ and water, whereas Au NPs cannot. For alcohol oxidation, the reducibility of the MO supports greatly influences the catalytic activity of Au, and single Au atoms more effectively activate the lattice oxygen of CeO₂. The basic and acidic sites of the MO surface also play an important role in the deprotonation of alcohols and the activation of aldehydes, respectively. For selective hydrogenation, heterolytic dissociation of H₂ takes place at the interface between Au and MO, and the basic sites of MO contribute to H₂ activation. Recent research into the reaction mechanisms and the development of well-designed Au catalysts has provided new insights into the preparation of high-performance Au catalysts.