Metal–supported catalysts encapsulated in mesoporous solids: Challenges and opportunities of a model concept



An overview of work with model systems designed to study metal–support interactions in heterogeneous catalysts is given. In these models, metal and support are both miniaturized by introduction as guests into a mesoporous host. The use of such models is demonstrated with Au[BOND]TiO2 clusters encaged in MCM-48, and Cu[BOND]ZnO clusters encapsulated in siliceous mesopore systems and in carbon nanotubes. The models promise a better opportunity to track changes in the support component during catalyst activation and catalysis, including the action of poisons that may at first be trapped on the support surface. Challenges to be met are the stabilization of the mesoporous matrix during synthesis and catalysis, possible reactivity of the matrix surface towards any of the catalyst components, as well as clustering and segregation of the latter from the matrix. The challenges were encountered as pore damage during preparation of Au[BOND]TiO2/MCM-48 catalysts, as deactivating interactions of siliceous walls with zinc ions during deposition of zinc species from aqueous media, and as clustering of the Cu component during calcination and reduction. Among the conclusions drawn from the studies are the irrelevance of order at the Au[BOND]TiO2 interface (and, hence, of epitaxy and of crystal strain in gold) for high activity of Au/TiO2 catalysts in CO oxidation. In the models for Cu[BOND]ZnO methanol synthesis catalysts, two different types of Cu[BOND]Zn interaction could be observed: a direct contact between Zn2+ and Cu(0) under strong reducing conditions, and the formation of alloy nanoparticles (nano-brass). A discussion of the relevance of these interactions for the methanol synthesis reaction is given.