Microporous 3D-Structured Hierarchically Entangled Graphene-Supported Pt₃Co Alloy Catalyst for PEMFC Application with Process-Friendly Features

To improve the oxygen reduction reaction (ORR) performance in a proton-exchange membrane fuel cell (PEMFC) cathode with respect to mass activity and durability, a suitable electrocatalyst design strategy is essentially needed. Here, we have prepared a sub-three nm-sized platinum (Pt)–cobalt (Co) alloy (Pt₃Co)-supported N-doped microporous 3D graphene (Pt₃Co/pNEGF) by using the polyol synthesis method. A microwave-assisted synthesis method was employed to prepare the catalyst based on the 3D porous carbon support with a large pore volume and dense micro-/mesoporous surfaces. The ORR performance of Pt₃Co/pNEGF closely matches with the <i>state-of-the-art</i> commercial Pt/C catalyst in 0.1 M HClO₄, with a small overpotential of 10 mV. The 3D microporous structure of the N-doped graphene significantly improves the mass transport of the reactant and thus the overall ORR performance. As a result of the lower loading of Pt in Pt₃Co/pNEGF as compared to that in Pt/C, the alloy catalyst achieved 1.5 times higher mass activity than Pt/C. After 10,000 cycles, the difference in the electrochemically active surface area (ECSA) and half-wave potential (<i>E</i>_1/2) of Pt₃Co/pNEGF is found to be 5 m² g_Pt^–1 (ΔECSA) and 24 mV (Δ<i>E</i>_1/2), whereas, for Pt/C, these values are 9 m² g_Pt^–1 and 32 mV, respectively. Finally, in a realistic perspective, single-cell testing of a membrane electrode assembly (MEA) was made by sandwiching the Pt₃Co/pNEGF-coated gas diffusion layers as the cathode displayed a maximum power density of 800 mW cm^–2 under H₂–O₂ feed conditions with a clear indication of helping the system in the mass-transfer region (i.e., the high current dragging condition). The nature of the <i>I</i>–<i>V</i> polarization shows a progressively lower slope in this region of the polarization plot compared to a similar system made from its Pt/C counterpart and a significantly improved performance throughout the polarization region in the case of the system made from the Pt₃Co/NEGF catalyst (without the microwave treatment) counterpart. These results validate the better process friendliness of Pt₃Co/pNEGF as a PEMFC electrode-specific catalyst owing to its unique texture with 3D architecture and well-defined porosity with better structural endurance.