Supports can widely affect or even dominate the catalytic activity, selectivity, and stability of metal nanoparticles through various metal-support interactions (MSIs). However, underlying principles have not been fully understood yet, because MSIs are influenced by the composition, size, and facet of both metals and supports. Using Ru/TiO₂ supported on rutile and anatase as model catalysts, we demonstrate that metal-support interfacial compatibility can critically control MSI modes and catalytic performances in CO₂ hydrogenation. Annealing Ru/rutile-TiO₂ in air can enhance CO₂ conversion to methane resulting from enhanced interfacial coupling driven by matched lattices of RuO_x with rutile-TiO₂; annealing Ru/anatase-TiO₂ in air decreases CO₂ conversion and converts the product into CO owing to strong metal-support interaction (SMSI). Although rutile and anatase share the same chemical composition, we show that interfacial compatibility can basically modify metal-support coupling strength, catalyst morphology, surface atomic configuration, MSI mode, and catalytic performances of Ru/TiO₂ in heterogeneous catalysis.

We achieved successful synthesis of alloy nanoframes, including bi-metallic and tri-metallic nanoframes, which show superior catalytic properties toward OER.