Oxygen Reduction Reaction of Pt and Non-PGM Transition Metal High Entropy Alloys Single Crystal Stacking Structures
Authors: Chida Yoshihiro , Tomimori Takeru , Ebata Tomoaki , Taguchi Noboru , Ioroi Tsutomu , Todoroki Naoto , Wadayama Toshimasa 
Published: November 2022

Introduction

Nanoparticles of Pt as well as Pt-based alloys are widely used as cathode catalyst materials for proton exchange membrane fuel cells (PEMFC). However, electrochemical stability of the materials is rather low under practical operating conditions of PEMFC cathode, resulting in severe deactivation of oxygen reduction reaction (ORR). Therefore, further material’s developments are required for next-generation PEMFC cathode catalysts, i.e., more enhanced ORR durability with low platinum group metal (PGM) usage.
High entropy alloys (HEAs), defined as single phase solid solutions of five or more elements in equal composition ratios, are known as thermodynamically stable, in comparison to conventional binary alloys. Furthermore, complex atomic-level local structures bring about unique electronic as well as (electro-)chemical properties that originating from lattice strains induced by specific local structures and/or so-called sluggish diffusion of the constituent elements. [1] However, to our best knowledge, no study has been made for ORR properties of Pt alloying with non-PGM Cantor alloy (fcc structure HEA with equi-atomic ratio of Cr-Mn-Fe-Co-Ni [2]) elements in strong acid condition.
In this study, we synthesized lattice stacking structures of Pt/HEA(hkl) (hkl = (111), (110), (100)) through arc-plasma deposition (APD) of the Cantor alloy layer on Pt(hkl) substrate surfaces, followed by deposition of the surface Pt layer in ~10-7 Pa. Then, we performed cross-sectional STEM-EDS observations for Pt/HEA/Pt(hkl) stacking structures with atomic-level resolution and evaluated the ORR properties (initial activity and structural stability).

Experimental

An APD target of Cr-Mn-Fe-Co-Ni (Cantor alloy) was fabricated by sintering of equal quantity corresponding elements. 10 ML(monolayer)-thick (1 ML = ca. 0.3 nm) Cantor alloy layer (as HEA) was vacuum-deposited by APD on surface cleaned Pt(hkl) substrate surfaces at 300 K, and subsequently annealed in vacuum at 773 K for 30 minutes. Then, 4ML-thick Pt layer was deposited on the pre-deposited Cantor alloy layer at 300 K and annealed at 623 K. The samples thus prepared are designated as Pt/HEA/Pt(hkl). The atomic-level micro-structures and chemical bonding states of Pt/HEA/Pt(hkl) surfaces were characterized by cross-sectional STEM-EDS, RHEED, XPS etc. CV and LSV with the RDE method were conducted in N2-purged and O2-saturated 0.1 M HClO4. ORR activity was evaluated from j
k values at 0.9 V vs. RHE by using Koutecky-Levich equation and structural stability (ORR durability) was discussed based upon activity transitions during applying the potential cycles (PCs) of 0.6(3s)‐1.0(3s) V vs. RHE in O2 saturated 0.1 M HClO4 at room temperature.

Results and Discussion

Atomically-resolved, cross-sectional HAADF-STEM images for Pt/HEA/Pt(hkl) (a) and EDS line profiles of elemental distributions at corresponding yellow arrows (b) are presented in Figure 1. As clearly shown in (a), irrespective of the Pt surface indices, (hkl), HEA (Cantor alloy) and surface Pt layers are epitaxially grown on the substrates. By contrast, elemental distributions in each surface normal (b) seriously depend on the substrate Pt lattice indices. Notably, severe thermal diffusion of the constituent elements including Pt is confirmed by (a) and (b) for both Pt/HEA/Pt(110) and (100).
Figure 2 summarizes electrochemical results. 4ML-thick-Pt/10ML-thick-Co/Pt(hkl) that prepared under the same preparation condition of Pt/HEA/Pt(hkl), and clean Pt(hkl) (light blue and gray, respectively) are also shown as references. As shown in the figure, the Pt/HEA and Pt/Co fabricated on Pt(111) substrate (top) show quite similar CV characteristics (shrink in hydrogen adsorption charges (0 – 0.3 V) and higher potential shifts in oxygen-related species adsorption (0.6 – 1.0 V)), in comparison to clean Pt(111), and almost the same initial ORR activity. Meanwhile, the Pt/HEA fabricated on Pt(110) and (100) substrates show more reduced hydrogen absorption charges, compared with corresponding Pt/Co samples. Particularly, distinctive redox features for clean Pt(110) at 0.12 V and for Pt(100) at 0.35 V are absent for corresponding CVs, suggesting specific topmost surface atomic-structures might be formed in the electrolyte, that probably resulting from significant electronic interactions between surface Pt and HEA constituent elements (Cr, Mn, Fe, Co, Ni) and/or local strain of the surface Pt layer induced by distorted Pt-HEA lattices located nearby. One might notice that Pt/HEA/Pt(110) reveals remarkable ORR activity enhancement compared with corresponding Pt/Co/Pt(110), while the activities for Pt/HEA and corresponding Pt/Co surfaces fabricated on Pt(100) are almost the same value. At the meeting, correlations between surface atomic-level micro-structures of Pt/HEA/Pt(hkl) and ORR properties will be discussed in detail.

Acknowledgement

This study was supported by new energy and industrial technology development organization (NEDO) of Japan and JST SPRING, Grant Number JPMJJSP2114.
Reference
[1] J. Yeh, JOM, 65, 1759 (2013).
[2] B. Cantor et al., Mater. Sci. Eng. A, 375, 213 (2004).

Figure 1