Organometallic Synthesis of Platinum-Based Nanomaterials for the Oxygen Reduction Reaction

Pt-based catalysts remain the most effective materials for the oxygen reduction reaction (ORR) at the cathode of proton exchange membrane fuel cells (PEMFCs); however, platinum scarcity and high cost severely limit the large-scale deployment of the technology. Improving catalytic activity and durability through precise control of nanoparticle morphology is therefore crucial for reducing costs and enhancing sustainability, enabling PEMFC widespread adoption. In this context, carbon-supported Pt-based nanoparticles with a 30 wt.% Pt loading were synthesized by an organometallic chemistry approach using hexadecylamine (HDA) as a stabilizer, allowing fine control over nanoparticle morphology. Two distinct synthesis pathways (one-pot and two-step procedures) were used to prepare platinum catalysts supported on KetjenBlack EC-300J (KB), and their influence on the electrocatalytic activity of the obtained nanomaterials was studied. Furthermore, the effect of HDA stabilization on catalyst performance was investigated. Directly synthesized Pt/KB catalysts exhibited similar ORR mass activity, regardless of whether or not HDA was present. Pt/KB prepared by the two-step procedure showed a significantly lower performance. Additionally, despite a larger loss of electrochemical surface area during an accelerated stress test compared to a commercial Pt/C reference, Pt^HDA/KB and Pt/KB catalysts maintained stable mass activity and limited specific activity degradation, highlighting the beneficial effect of nanoparticle stabilization in the presence of HDA on prolonged electrocatalyst cycling.