High-Entropy Alloys as Oxygen Reduction Reaction Electrocatalysts for Proton Exchange Membrane Fuel Cells Application

High entropy alloys (HEA) are complex multi-element materials. Owing to their multi-elemental nature, they can finetune surface adsorption energy and active sites which make them appealing to various catalytic reactions. HEI is a subclass of HEA that consist of an ordered alloy structure rather than a random alloy structure. The order-ness may induce more stable structures and uniform active sites, which in turn enhance the durability and activity under catalytic conditions. Here, we have synthesized a HEI(Pt40Ni20Co20Mn10Ir10) supported on porous carbon via a seed-mediated impregnation method. The intermetallic characteristics with periodic trends can be seen in the HAADF-STEM image (Fig. 1a). Based on the atomic arrangement, the HEI resembled a L12 structure. The corresponding EDX mapping the catalyst also showed the presence of all alloying species in the nanoparticles. The catalyst performance of the catalysts was evaluated in a 3-electrode liquid cell set-up with catalyst coated glassy carbon rotating disk electrode, Ag/AgCl and Pt mesh as working, reference and counter electrode, respectively. The catalyst’s mass activity (MA) was calculated based on the result obtained from ORR polarization test conducted under O2 saturated 0.1M HClO4. The initial mass activities for PtCo and HEA in ORR were 0.81 and 1.23 A mg-1 Pt, respectively (Fig. 1b), while that of Pt/C was only 0.26 A mg-1 Pt. A subsequent accelerated degradation test (ADT) was conducted under Ar-saturated 0.1M HClO4 with 0.6-1.0 V vs RHE square-wave cycling (3s hold at each potential) for 30k cycles. MA was measured after 10k and 30k cycles. HEA retained a MA of 0.48 A mg-1 Pt after the ADT, above the DOE target (0.44 A mg-1 Pt). We also compared our HEI samples synthesized with different annealing temperatures and duration (Fig. 1c), and it showed that 800◦C with 20 mins temperature hold showed the highest MA and electrochemical surface area (ECSA). Extended X-ray absorption spectroscopy (EXAFS) for the catalyst has also been conducted to further elucidate the structural-performance relationship of HEI (Fig.1d). From Pt L3 edge EXAFS fitting, the fitted R space showed that the Pt-Pt bond length was around 2.704 ± 0.004 Å, which was same as that of the PtCo (Fig. 1e). Therefore, it is believed that both HEI and PtCo has the same strain effect but HEI possessed stronger ligand effect than PtCo due to its unique Pt-M coordination, hence resulting in superior ORR performance over PtCo and Pt. Figure 1