PNNL

Abstract

Single-atom catalysts are often reported to have catalytic properties that surpass those of nanoparticles, while a direct comparison of sites common and different for both is lacking. Here we show that single atoms of the Pt-group embedded into the surface of Fe3O4 have a greatly enhanced interaction strength with CO2 compared with Fe3O4 surface. The strong CO2 adsorption on single Rh atoms and corresponding low activation energies lead to two-orders-of-magnitude higher conversion rates of CO2 compared to Rh nanoparticles. This high activity of single atoms stems from the partially oxidic state imposed by their coordination to the support. Fe3O4-supported Rh nanoparticles follow the behavior of single atoms for CO2 interaction and reduction, which is attributed to the dominating role of partially oxidic sites at the Fe3O4-Rh interface. Thus, we show a likely common catalytic chemistry for two kinds of materials thought to be different, and we show that single atoms of Pt-group metals on Fe3O4 are an especially successful material for catalyzed reactions that depend primarily upon sites with the metal-O-Fe environment.