The Role of an Organic Cap in Nanoparticle Catalysis: Reversible Restructuring of Carbonaceous Material Controls Catalytic Activity of Platinum Nanoparticles for Ethylene Hydrogenation and Methanol Oxidation

Inherent in the colloidal synthesis of nanopar- ticle catalysts is the presence of an organic capping agent that encapsulates the nanoparticles to prevent aggregation. However, this capping agent often remains present on the nanoparticles during catalytic reaction, and the effect of this coating on catalysis is an important question that will influence the future applications of colloidal nanoparticles. In this study, the structure of poly(vinylpyrrolidone) (PVP) ligands on Pt nanoparticles is probed using sum frequency generation vibrational spectroscopy before and after cap removal by UV light. When the PVP is removed, carbo- naceous fragments remain on the surface that dynamically restructure in H2 and O2. These fragments form a porous coating around the Pt in H2 but collapse to a tightly closed shell in O2. Using ethylene hydrogenation and methanol oxidation as a probe for the catalytic activity of the nanoparticles in H2 and O2, respectively, it is shown that the structure of these carbonaceous fragments controls the catalytic activity of the nanoparticles across several orders of magnitude by opening in H2 and collapsing to block Pt sites in O2. Kinetic experiments on thermally-cleaned PVP- capped and oleic acid-capped nanoparticles show that these findings apply to multiple capping agents and cleaning methods. This work highlights the dominant role of an organic cap to mediate nanoparticle catalysis and provides one example where capped nanoparticles are dramatically better catalysts than their uncapped analogues.