Electron-level insight into efficient synergistic oxygen evolution catalysis at multimetallic sites in PtNiFeCoCu high-entropy alloys

Abstract

The exploration of high-quality and efficient electrocatalysts is crucial for the advancement of clean energy utilization and the development of energy conversion technologies. Recently, high-entropy alloys (HEA) have been actively explored as viable catalysts for water electrolysis due to their unique performance such as wide scope for compositional adjustments, excellent catalytic activity, and outstanding stability. However, the mechanism of synergistic oxygen evolution by HEA electrocatalysts at multiple sites has not been systematically and clearly demystified. Herein, in this paper, Pt is combined with inexpensive metals Ni, Cu, Fe, and Co to form a stable HEA structure. The synergistic catalytic mechanism of the PtNiFeCoCu HEA in the oxygen evolution reaction (OER) has been investigated, and the structure has been demonstrated to exhibit excellent hydrogen evolution reaction (HER) activity. The results suggest that the PtNiFeCoCu HEA catalyst achieved a lower overpotential of 0.44 V in the acidic OER, demonstrating that the PtNiFeCoCu HEA is a bifunctional electrocatalyst. In addition, oxygen intermediates are synergistically adsorbed on the surface of high-entropy alloys through multimetallic sites, which breaks the limitation of limited active sites. Further calculations indicated that the favorable OER activity of the catalyst originated from the strong associative coupling of the d orbitals of the synergistic metal sites to the 2p orbitals of the oxygen intermediates with enhanced synergistic effects. This work further elucidates the multisite synergistic catalysis of the PtNiFeCoCu HEA, providing a unique perspective to uncover the source of the high catalytic performance of HEA electrocatalysts.