Oxygen reduction reaction and proton exchange membrane fuel cell performance of pulse electrodeposited Pt–Ni and Pt–Ni–Mo(O) nanoparticles

Proton exchange membrane fuel cells (PEMFCs) are an important alternative to fossil fuels and a complement to batteries for the electrification of vehicles. However, their high cost obstructs commercialization, and the catalyst material, including its synthesis, constitutes one of the major cost components. In this work, Pt–Ni and Pt–Ni–Mo(O) nanoparticles (NPs) of varying composition have been synthesized in a single step by pulse electrodeposition onto a PEMFC's gas diffusion layer. The proposed synthesis route combines NP synthesis and their fixation onto the microporous carbon layer in a single step. Both Pt–Ni and Pt–Ni–Mo(O) catalysts exhibit extremely high mass activities at oxygen reduction reaction (ORR) with very low Pt loadings of around 4 μg/cm2 due to the favorable distribution of NPs in contact with the proton exchange membrane. Particle sizes of 40–50 nm and 40–80 nm were obtained for Pt–Ni and Pt–Ni–Mo(O) systems, respectively. The highest ORR mass activities were found for Pt67Ni33 and Pt66Ni32–MoOx NPs. The feasibility of a single-step electrodeposition of Pt–Ni–Mo(O) NPs was successfully demonstrated; however, the ternary NPs are of more amorphous nature in contrast to the crystalline, binary Pt–Ni particles, due to the oxidized state of Mo. Nevertheless, despite their heterogeneous nature, the ternary NPs show homogeneous behavior even on a microscopic scale.