Adsorbate-mediated strong metal–support interactions in oxide-supported Rh catalysts

The optimization of supported metal catalysts predominantly focuses on engineering the metal site, for which physical insights based on extensive theoretical and experimental contributions have enabled the rational design of active sites. Although it is well known that supports can influence the catalytic properties of metals, insights into how metal–support interactions can be exploited to optimize metal active-site properties are lacking. Here we utilize in situ spectroscopy and microscopy to identify and characterize a support effect in oxide-supported heterogeneous Rh catalysts. This effect is characterized by strongly bound adsorbates (HCOx) on reducible oxide supports (TiO2 and Nb2O5) that induce oxygen-vacancy formation in the support and cause HCOx-functionalized encapsulation of Rh nanoparticles by the support. The encapsulation layer is permeable to reactants, stable under the reaction conditions and strongly influences the catalytic properties of Rh, which enables rational and dynamic tuning of CO2-reduction selectivity. Developing approaches to tune the reactivity and selectivity of supported-metal heterogeneous catalysts is critical for designing environmentally friendly chemical conversion processes. A reversible structural catalyst transformation has now been identified that involves the adsorbate-mediated encapsulation of Rh nanoparticles by their oxide support and enables dynamic tuning of the selectivity of CO2 reduction.