(Invited) Extended Thin Film Platinum Group Metal Electrocatalysts with Different Mesoscale Morphologies

Abstract

The lack of sufficiently active oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) electrocatalysts is a bottleneck to the proliferation of PEM fuel cells and water electrolyzers. Commercially available PGM electrocatalysts fail to attain DOE technical targets due to instabilities and activity losses incurred at low loadings. Morphology control of PGM nanostructures is an enticing route towards activity and stability enhancements of electrocatalysts, but not much is known about the structure-property relationships between PGM mesoscale geometry (5 to 100 nm) and their activity and stability.This talk presents our work on model Pt extended surface electrocatalysts of tunable feature sizes and morphologies prepared from self-assembled block copolymer templates. The morphology, either perpendicular lamellae, cylinders, or perforated cylinders, of the extended surface electrocatalyst was controlled by the block copolymer volume fraction. The periodic lateral feature sizes (10 to 40 nm in this work) were controlled by the block copolymer degree of polymerization. The self-assembled block copolymers were transformed into extended surfaces using sequential infiltration synthesis to prepare aluminum oxide followed by reactive ion etching to remove the block copolymer template. Pt was sputtered onto the aluminum oxide supports. ORR data in a RDE with the new extended nanostructured thin films of Pt showed mass activity values of 0.35 A mgPt-1 to 0.46 A mgPt -1 at 0.9 V vs. RHE. The measured electro-chemically active surface area (ECSA) values obtained from hydrogen underpotential deposition were 64 to 70 m2 gPt -1. The lower values hailed from lamellae morphology while the larger values corresponded to a cylindrical morphology. The measured mass activity values, which have no cobalt or nickel additives and are unoptimized and display competitive mass activity values for ORR. We envision that the block copolymer templated extended surfaces could be an alternative to 3M’s state-of-the-art nanostructured thin film technology.