Tuning the electronic structure of Ag-Pd alloys to enhance performance for alkaline oxygen reduction.

Zamora Zeledón, José A; Stevens, Michaela Burke; Gunasooriya, G T Kasun Kalhara; Gallo, Alessandro; Landers, Alan T; Kreider, Melissa E; Hahn, Christopher; Nørskov, Jens K et al. · Nat Commun · 2021

basic_science · Level V

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Abstract

Alloying is a powerful tool that can improve the electrocatalytic performance and viability of diverse electrochemical renewable energy technologies. Herein, we enhance the activity of Pd-based electrocatalysts via Ag-Pd alloying while simultaneously lowering precious metal content in a broad-range compositional study focusing on highly comparable Ag-Pd thin films synthesized systematically via electron-beam physical vapor co-deposition. Cyclic voltammetry in 0.1 M KOH shows enhancements across a wide range of alloys; even slight alloying with Ag (e.g. Ag<sub>0.1</sub>Pd<sub>0.9</sub>) leads to intrinsic activity enhancements up to 5-fold at 0.9 V vs. RHE compared to pure Pd. Based on density functional theory and x-ray absorption, we hypothesize that these enhancements arise mainly from ligand effects that optimize adsorbate-metal binding energies with enhanced Ag-Pd hybridization. This work shows the versatility of coupled experimental-theoretical methods in designing materials with specific and tunable properties and aids the development of highly active electrocatalysts with decreased precious-metal content.