Impact of Carbon N-Doping and Pyridinic-N Content on the Fuel Cell Performance and Durability of Carbon-Supported Pt Nanoparticle Catalysts.

Abstract

Cathode catalyst layers of proton exchange membrane fuel cells (PEMFCs) typically consist of carbon-supported platinum catalysts with varying weight ratios of proton-conducting ionomers. N-Doping of carbon support materials is proposed to enhance the performance and durability of the cathode layer under operating conditions in a PEMFC. However, a detailed understanding of the contributing N-moieties is missing. Here, we report the successful synthesis and fuel cell implementation of Pt electrocatalysts supported on N-doped carbons, with a focus on the analysis of the N-induced effect on catalyst performance and durability. A customized fluidized bed reduction reactor was used to synthesize highly monodisperse Pt nanoparticles deposited on N-doped carbons (N-C), the catalytic oxygen reduction reaction activity and stability of which matched those of state-of-the-art PEMFC catalysts. Operando high-energy X-ray diffraction experiments were conducted using a fourth generation storage ring; the light of extreme brilliance and coherence allows investigating the impact of N-doping on the degradation behavior of the Pt/N-C catalysts. Tests in liquid electrolytes were compared with tests in membrane electrode assemblies in single-cell PEMFCs. Our analysis refines earlier views on the subject of N-doped carbon catalyst supports: it provides evidence that heteroatom doping and thus the incorporation of defects into the carbon backbone do not mitigate the carbon corrosion during high-potential cycling (1-1.5 V) and, however, can promote the cell performance under usual PEMFC operating conditions (0.6-0.9 V).