Influence of surface capping on oxygen reduction catalysis: A case study of 1.7 nm Pt nanoparticles

Abstract

Organic and polymer capping agents are prevailingly used in the synthesis of metal nanocrystals to render size and shape controls for desirable catalytic properties. A general assumption in the electrocatalysis field is that the capping agents block active sites and hinder catalytic turnover. However there have been a number of experimental results suggesting otherwise. Investigation of the fundamental correlations between the surface capping and the catalytic kinetics of metal nanoparticles is of paramount importance yet still remains challenging in large part due to structural changes induced by capping agent removal or synthesis using different capping agents. Our approach involves a unique catalyst system comprising of 1.7nm Pt nanoparticles with and without various surface capping. We find that surface capping affects both activity and selectivity of electrocatalytic oxygen reduction reaction. The influences can be positive, neutral or negative. The five capping agents studied fall into three groups. Polyacrylic acid (PAA) and polyvinylpyrrolidone (PVP) cappings do not change the onset potential or product selectivity, but increase the catalytic current density. Sodium dodecyl sulfate (SDS) and tetradecyltrimethylammonium bromide (TTAB) cappings do not change the onset potential or product selectivity, but slightly decrease the catalytic current density. Oleylamine (OA) capping significantly decreases the onset potential and the catalytic current density as well as change the product selectivity by favoring a high percentage of 2-electron reduction.